US3874957A - Use of 1,1'-bis-(1-glycidoxylalkyl) ferrocenes in rocket propellants - Google Patents
Use of 1,1'-bis-(1-glycidoxylalkyl) ferrocenes in rocket propellants Download PDFInfo
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- US3874957A US3874957A US031041A US3104170A US3874957A US 3874957 A US3874957 A US 3874957A US 031041 A US031041 A US 031041A US 3104170 A US3104170 A US 3104170A US 3874957 A US3874957 A US 3874957A
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- 239000003380 propellant Substances 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 abstract description 35
- -1 alkali metal salt Chemical class 0.000 abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000001266 acyl halides Chemical class 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 125000005417 glycidoxyalkyl group Chemical group 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- RDFMMZXTHFHHQT-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-ylethanol;iron(2+) Chemical compound [Fe+2].CC(O)C1=CC=C[CH-]1.CC(O)C1=CC=C[CH-]1 RDFMMZXTHFHHQT-UHFFFAOYSA-N 0.000 description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 3
- 239000012280 lithium aluminium hydride Substances 0.000 description 3
- 239000004449 solid propellant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WDKIARLEQFHVKC-UHFFFAOYSA-N 1-cyclopenta-1,3-dien-1-ylethanone;iron(2+) Chemical compound [Fe+2].CC(=O)C1=CC=C[CH-]1.CC(=O)C1=CC=C[CH-]1 WDKIARLEQFHVKC-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
Definitions
- ABSTRACT 1,1'-Bis(1,glycidoxyalkyl)ferrocenes are new compounds prepared by (a) reacting an acyl halide with ferrocene to form a 1,1 '-bis(acyl)ferrocene, (b) reducing the 1,1'-bis(acy1)ferrocene to a 1,1'-bis(1- hydroxya1ky1)ferrocene with a reducing agent, (c) reacting the l,1-bis(1-hydroxyalkyl)ferrocene with an alkali metal alkyl to form the alkali metal salt, and (d) reacting the alkali metal salt with an epihalohydrin to form the final product.
- the 1,1 -bis( l-glycidoxyalkyl)- ferrocenes are useful as curing agents for solid rocket propellant binders,
- This invention relates to new ferrocene compounds and to a method for their preparation. In one aspect it relates to solid rocket propellants containing the ferrocene compounds.
- Ferrocene derivatives have been suggested for use as combustion catalysts for rocket propellants. However, the use of such compounds has not been satisfactory because, in general, the prior art ferrocene derivatives have been low molecular weight, highly volatile compounds. And when they have been incorporated into rocket propellants, they have exhibited a strong tendency to migrate away from the propellant grain into other parts of the rocket engine during storage. Thus, the search has gone on for new ferrocene derivatives which retain desirable properties, e.g., the ability to catalyze combustion, and which may be utilized in solid rocket propellants without exhibiting a tendency to migrate.
- R is selected from the group consisting of hydrogen and alkyl.
- the alkyl group generally contains from 1 to 8 carbon atoms, preferably from 1 to 2 carbon atoms. They are prepared from ferrocene utilizing the following reactions wherein R is the same as above:
- acyl halide LtalLSL R E; u v O alkali metal alkyl epihalohydr'in M in the above formulas is a symbol designating an alkali metal ion such as Li*, Na, or K.
- Methods of chemically tieing the compounds to solid propellant grains include (a) utilizing them as curing agents for hydroxy or carboxy terminated propellant binders, (b) precipitating them as homopolymer coats on oxidizer crystals prior to the incorporation of the crystals into solid propellant grains, and (c) introducing them as liquid plasticizers during the propellant mix cycle wherein they homopolymerize into high molecular weight, nonmigrating compounds.
- 1,1'-Bis(acetyl)ferrocene is prepared by reacting acetyl chloride with ferrocene in the presence of aluminum chloride.
- a ratio of 1 equivalent of ferrocene to 3 equivalents of acetyl chloride and 3 equivalents of the aluminum chloride catalyst are mixed in dry methylene chloride under a nitrogen atmosphere. The mixture is refluxed for about 18 to 24 hours and then hydrolyzed with de-oxygenated water and extracted with chloroform. Needles of 1,1-bis(acetyl)ferrocene form in and separate from the chloroform.
- 1,1 '-Bis( l-hydroxyethyl)ferrocene is prepared by mixing 1,1 -bis(acetyl)ferrocene 15.0 g, 0.0555 mole) and lithium aluminum hydride (1.5 g) in 120 ml of dry tetrahydrofuran. The mixture is stirred and refluxed for about 1 to 2 hours. After refluxing, ethyl acetate is added to destroy any excess lithium aluminum hydride. Then a mixture of 3.5 ml water, 25 ml ethanol, and 50 ml ether is cautiously added to the mixture and the mixture is filtered. The filtrate is then subjected to reduced pressure to remove solvents.
- 1,1'-bis(l-hydroxyethyl)ferrocene which remains as an oil is taken up in hot hexane. Cooling of the hexane solution in a dry ice bath yields about 70% of theoretical of 1,1 '-bis( l-hydroxyethyl)ferrocene needles which are separated from the hexane by filtration.
- EXAMPLE IV STEP 4 The final step in the preparation of l,1'-bis(lglycidoxyethyl)ferrocene is the addition of epibromohydrin (3.2 g, 20 m moles) to the reaction mixture of EXAMPLE Ill.
- the epibromohydrin is added dropwise and followed by the addition of ml of dimethylsulfoxide.
- the mixture is then refluxed for from 5 4 to 5 hours, poured onto ice, and extracted with ether.
- a solution of the product in ether forms a layer separate from the rest of the mixture and is separated therefrom.
- the ethereal solution is washed first with water and then with a saturated sodium chloride solution and then dried over magnesium sulfate.
- the ether is then evaporated under reduced pressure.
- X is a halide such as C1 or Br for the acetyl chloride of EXAMPLE 1. Any desirable isomer of the alkyl group may be used.
- Other Lewis acids may be used as catalysts in lieu of the aluminum chloride of EXAMPLE 1.
- Other reducing agents such as sodium borohydride may be used in lieu of the lithium aluminum hydride of EXAMPLE I].
- Other alkali metal alkyls such as n-pentyllithium and n-propyllithium and their sodium and potassium derivatives may be used in lieu of the n-butyllithium of EXAMPLE III.
- epichlorohydrin may be used in lieu of the epibromohydrin of EXAMPLE IV.
- EXAMPLE V l,l'-Bis( l-glycidoxyethyl)ferrocene as Curing Agent
- the cured sample was compared with one in which the 1,1'-bis(l-glycidoxyethyl)ferrocene was replaced with an equivalent amount of a standard curing agent, Union Carbide ERL 4221 (diepoxide) and which was cured under identical conditions. Both cured samples were rubbery materials. The sample utilizing 1,l '-bis( l-glycidoxyethyl)ferrocene was softer.
- the 1,l'-bis( l-glycidoxyalkyl)ferrocenes may also be used to coat fuels, such as aluminum, prior to incorporation into a propellant mix cycle.
- a new composition of matter comprising a solid rocket propellant binder and a curing agent having the general formula:
- a solid rocket propellant comprising a cured binder containing fuel and oxidizer particles and a homopolymer of a compound having the general formula:
- R is selected from the group consisting of H
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1,1''-Bis(1,glycidoxyalkyl)ferrocenes are new compounds prepared by (a) reacting an acyl halide with ferrocene to form a 1,1''bis(acyl)ferrocene, (b) reducing the 1,1''-bis(acyl)ferrocene to a 1,1''-bis(1-hydroxyalkyl)ferrocene with a reducing agent, (c) reacting the 1,1''-bis(1-hydroxyalkyl)ferrocene with an alkali metal alkyl to form the alkali metal salt, and (d) reacting the alkali metal salt with an epihalohydrin to form the final product. The 1,1''-bis(1-glycidoxyalkyl)ferrocenes are useful as curing agents for solid rocket propellant binders, as plasticizers for solid rocket propellants, and as burn rate catalysts.
Description
United States Patent 1191 Corley et a1.
[ USE OF 1,1'-BlS-(l-GLYCIDOXYLALKYL) FERROCENES IN ROCKET PROPELLANTS [75] Inventors: Robert C. Corley, Lancaster, Calif.;
Fred M. Dewey, Denver, C010.
[73] Assignee: The United States of America as represented by the Secretary of the Air Force, Washington, DC.
22 Filed: Apr. 7, 1970 211 Appl. No: 31,041
[52] U.S. Cl 149/5, 149/7, 149/19.2, 149/44, 260/348 R, 260/439 CY [51] Int. Cl C06b 19/02 [58] Field of Search 260/348 R; 149/5, 7, 19, 149/l9.2
[56] References Cited UNITED STATES PATENTS 3,437,634 4/1969 Neuse 260/47 3,598,850 8/1971 Dewey 260/439 OTHER PUBLICATIONS Adams et 211., Organic Reactions, Vol. 17, John Wiley 1451 Apr. 1, 1975 & Sons, Inc., New York, 1969, pp. 1 to 5, OD 251 07.
Primary ExaminerLeland A. Sebastian Attorney, Agent, or Firm-Harry A. Herbert, Jr.; Cedric H. Kuhn [57] ABSTRACT 1,1'-Bis(1,glycidoxyalkyl)ferrocenes are new compounds prepared by (a) reacting an acyl halide with ferrocene to form a 1,1 '-bis(acyl)ferrocene, (b) reducing the 1,1'-bis(acy1)ferrocene to a 1,1'-bis(1- hydroxya1ky1)ferrocene with a reducing agent, (c) reacting the l,1-bis(1-hydroxyalkyl)ferrocene with an alkali metal alkyl to form the alkali metal salt, and (d) reacting the alkali metal salt with an epihalohydrin to form the final product. The 1,1 -bis( l-glycidoxyalkyl)- ferrocenes are useful as curing agents for solid rocket propellant binders, as plasticizers for solid rocket propellants, and as burn rate catalysts.
4 Claims, N0 Drawings USE OF 1,1 -BIS-(1-GLYCIDOXYLALKYL) FERROCENES IN ROCKET PROPELLANTS I RIGHTS OF THE GOVERNMENT The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to new ferrocene compounds and to a method for their preparation. In one aspect it relates to solid rocket propellants containing the ferrocene compounds.
2. Description of the Prior Art Ferrocene derivatives have been suggested for use as combustion catalysts for rocket propellants. However, the use of such compounds has not been satisfactory because, in general, the prior art ferrocene derivatives have been low molecular weight, highly volatile compounds. And when they have been incorporated into rocket propellants, they have exhibited a strong tendency to migrate away from the propellant grain into other parts of the rocket engine during storage. Thus, the search has gone on for new ferrocene derivatives which retain desirable properties, e.g., the ability to catalyze combustion, and which may be utilized in solid rocket propellants without exhibiting a tendency to migrate.
"-H II o H Fe SUMMARY OF THE INVENTION A class of ferrocene derivatives which may be utilized in solid rocket propellants without migration has now been discovered. The ferrocene derivatives of this invention have two epoxy groups per molecule which provide reactive sites which enable them to be chemically tied to solid propellant grains in several ways and thus prevent migration while a propellant containing them is in storage. The general formula of the compounds is:
wherein R is selected from the group consisting of hydrogen and alkyl. The alkyl group generally contains from 1 to 8 carbon atoms, preferably from 1 to 2 carbon atoms. They are prepared from ferrocene utilizing the following reactions wherein R is the same as above:
acyl halide LtalLSL R E; u v O alkali metal alkyl epihalohydr'in M in the above formulas is a symbol designating an alkali metal ion such as Li*, Na, or K. Methods of chemically tieing the compounds to solid propellant grains include (a) utilizing them as curing agents for hydroxy or carboxy terminated propellant binders, (b) precipitating them as homopolymer coats on oxidizer crystals prior to the incorporation of the crystals into solid propellant grains, and (c) introducing them as liquid plasticizers during the propellant mix cycle wherein they homopolymerize into high molecular weight, nonmigrating compounds.
DESCRIPTION OF THE PREFERRED EMBODIMENT The preparation of the ferrocene derivatives of this invention may be conveniently described by selecting a specific compound and describing its preparation. The preparation of l, 1 '-bis( l-glycidoxyethyl)ferrocene is described in EXAMPLES I-IV below. It will be obvious to those skilled in the art that other similar derivatives may be prepared by substituting other acyl halides for the acetyl halide of EXAMPLE I.
EXAMPLE I STEP 1 1,1'-Bis(acetyl)ferrocene is prepared by reacting acetyl chloride with ferrocene in the presence of aluminum chloride. A ratio of 1 equivalent of ferrocene to 3 equivalents of acetyl chloride and 3 equivalents of the aluminum chloride catalyst are mixed in dry methylene chloride under a nitrogen atmosphere. The mixture is refluxed for about 18 to 24 hours and then hydrolyzed with de-oxygenated water and extracted with chloroform. Needles of 1,1-bis(acetyl)ferrocene form in and separate from the chloroform. When the needles are filtered out of the chloroform, washed with dilute sodium carbonate, and dried over anhydrous sodium sulfate, a yield of about 70% of theoretical of l,l'-bis- (acetyl)ferrocene is obtained.
EXAMPLE II STEP 2 1,1 '-Bis( l-hydroxyethyl)ferrocene is prepared by mixing 1,1 -bis(acetyl)ferrocene 15.0 g, 0.0555 mole) and lithium aluminum hydride (1.5 g) in 120 ml of dry tetrahydrofuran. The mixture is stirred and refluxed for about 1 to 2 hours. After refluxing, ethyl acetate is added to destroy any excess lithium aluminum hydride. Then a mixture of 3.5 ml water, 25 ml ethanol, and 50 ml ether is cautiously added to the mixture and the mixture is filtered. The filtrate is then subjected to reduced pressure to remove solvents. After removal of the solvents, 1,1'-bis(l-hydroxyethyl)ferrocene which remains as an oil is taken up in hot hexane. Cooling of the hexane solution in a dry ice bath yields about 70% of theoretical of 1,1 '-bis( l-hydroxyethyl)ferrocene needles which are separated from the hexane by filtration.
EXAMPLE III STEP 3 To prepare the lithium salt of l,l-bis(l-hydroxyethyl)ferrocene, the alcohol (0.5 g, 1.8 m moles) is dissolved in 20 ml of tetrahydrofuran and treated with 7.8 m moles of n-butyllithium (22.7 weight percent in hexane). The lithium salt of 1,1 -bis( l-hydroxyethyl)ferrocene which forms is left in the reaction mixture for use in the final step of the process.
EXAMPLE IV STEP 4 The final step in the preparation of l,1'-bis(lglycidoxyethyl)ferrocene is the addition of epibromohydrin (3.2 g, 20 m moles) to the reaction mixture of EXAMPLE Ill. The epibromohydrin is added dropwise and followed by the addition of ml of dimethylsulfoxide. The mixture is then refluxed for from 5 4 to 5 hours, poured onto ice, and extracted with ether.
A solution of the product in ether forms a layer separate from the rest of the mixture and is separated therefrom. The ethereal solution is washed first with water and then with a saturated sodium chloride solution and then dried over magnesium sulfate. The ether is then evaporated under reduced pressure. Column chromatography on alumina (hexane) gives an orange oil (0.4 g, 57 percent of theoretical): nmr(CDCl 4.38 (quartet, J= 6.5, 2H, C li(CH )--O), 4.14 (8H, ring protons), 3.54 (multiplet, 4l-l, OCl-I 3.10 (multiplet, 2H, epoxy CH), 2.67 (multiplet, 4H, epoxy CH and 1.53 ppm (doublet of doublets, J= 6.5 and 2, 6H, CH Analysis: Calculated for C l-I FeO C, 62.19; H, 6.79. Found: C, 61.82; H, 6.82.
The above EXAMPLES describe the preparation of 1,1 '-bis( 1-glycidoxyethyl)ferrocene, a compound wherein the R of the general formula is a methyl group. Other derivations wherein R is H, C I'I C l-l C I-I C ll C H, C l-l and C 11 may be prepared by substituting respectively O O O 0 U U U c ir j e-x,
and
wherein X is a halide such as C1 or Br for the acetyl chloride of EXAMPLE 1. Any desirable isomer of the alkyl group may be used. Other Lewis acids may be used as catalysts in lieu of the aluminum chloride of EXAMPLE 1. Other reducing agents such as sodium borohydride may be used in lieu of the lithium aluminum hydride of EXAMPLE I]. Other alkali metal alkyls such as n-pentyllithium and n-propyllithium and their sodium and potassium derivatives may be used in lieu of the n-butyllithium of EXAMPLE III. And finally, epichlorohydrin may be used in lieu of the epibromohydrin of EXAMPLE IV.
Methods of incorporating 1,1 '-bis( l-glycidoxyalkyl)- ferrocenes into solid rocket propellant grains are described in the following EXAMPLES. For convenience, l,1'-bis(1-glycidoxyethyl)ferrocene is designated as the ferrocene derivative incorporated.
EXAMPLE V l,l'-Bis( l-glycidoxyethyl)ferrocene as Curing Agent A mixture of 0.1 equivalent (109.5 g) carboxy terminated polybutadiene, 0.08 equivalent (14.6g) 1,1 bis( l-glycidoxyethyl)ferrocene, 0.02 equivalent (2.5 g) triepoxide, and 1 percent by weight chromium octoate was mixed under vacuum for 0.5 hour and then cured at 60C for 3 days. The cured sample was compared with one in which the 1,1'-bis(l-glycidoxyethyl)ferrocene was replaced with an equivalent amount of a standard curing agent, Union Carbide ERL 4221 (diepoxide) and which was cured under identical conditions. Both cured samples were rubbery materials. The sample utilizing 1,l '-bis( l-glycidoxyethyl)ferrocene was softer.
EXAMPLE Vl l,l'-Bis( l-glycidoxyethyl)ferrocene as Coating on Oxidizer Crystals Oxidizer crystals such as ammonium perchlorate are coated with l,1'-bis(l-glycidoxyethyl)ferrocene by.
Ingredient Weight Coated Ammonium Perchlorate 73 Aluminum Powder l5 Carboxy Terminated Polybutadiene l 1.5 Epoxy Curing Agent 0.5
The 1,l'-bis( l-glycidoxyalkyl)ferrocenes may also be used to coat fuels, such as aluminum, prior to incorporation into a propellant mix cycle.
EXAMPLE VII 1,1 '-Bis( l-glycidoxyethyl)ferrocene as Plasticizer Liquid 1,1'-bis(1-glycidoxyethyl)ferrocene is added to a propellant mix which may be of the following general formulation:
Ingredient Weight Ammonium Perchlorate 70 Aluminum Powder l5 Hydroxy Terminated Polybutadiene l0.5 Triisocyanate Curing Agent 0.5 l ,l '-Bis( l-glycidoxyethyl )ferrocene 4 The propellant mix is processed by well-known techniques. During the cure cycle the ferrocene derivative undergoes homopolymerization to yield a high molecular weight, nonmigrating compound.
While 1,1-bis(l-glycidoxyethyl)ferrocene has been used as a specific compound in the foregoing EXAM- PLES, it will be apparent to those skilled in the art that any of the other derivatives disclosed in this specification can be used with similar results.
What is claimed is:
1. A new composition of matter comprising a solid rocket propellant binder and a curing agent having the general formula:
wherein R is selected from the group consisting of H, and alkyls having the formulas CH C H C -,H C H s n G ISa 1 15 and s u- 2. A solid rocket propellant comprising a cured binder containing fuel and oxidizer particles and a homopolymer of a compound having the general formula:
wherein R is selected from the group consisting of H,
and alkyls having the formulas CH C 14 C l-l C l-l 5 11 C6H13, 1 15 and s n- 3. A propellant according to claim 2 wherein said homopolymer is coated on said oxidizer particles.
4. A propellant according to claim 2 wherein said homopolymer is coated on said fuel particles.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 5 DATED A ril 1,.1975
'NVENTOR(5) 3 Robert C. Corley et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In the drawings, cancel all figures, including the figure on the cover page.
Signed and Skilled this fif ay of August1975 [SEAL] A lies I:
RUTH C. MASON C. MARSHALL DANN Arresting Officer ('mnmissr'mu'r of Parents and Trademarks UNITED STATES PATENT OFFICE @ERTTTTCATE 6F QURRECTTQN PATENT NO. 13, 74,957
DATED April 1, 1975 INVENTOWS) T Robert C. Corley et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Q
In the drawings, cancel all figures, including the figure on the cover page,
0 $1'gned and geaied this fifth Day 0? August 1975 {SEAL} Arrest:
RUTH C. MASON C. MARSHALL DANN Alu'slmg Officer (mnmissr'mwr uj'lurems and Trademarks
Claims (4)
1. A new composition of matter comprising a solid rocket propellant binder and a curing agent having the general formula:
2. A SOLID ROCKET PROPELLANT COMPRISING A CURED BINDER CONTAINING FUEL AND OXIDIZER PARTICLES A HOMOPOLYMER OF A COMPOUND HAVING THE GENERAL FORMULA:
3. A propellant according to claim 2 wherein said homopolymer is coated on said oxidizer particles.
4. A propellant according to claim 2 wherein said homopolymer is coated on said fuel particles.
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US031041A US3874957A (en) | 1970-04-07 | 1970-04-07 | Use of 1,1'-bis-(1-glycidoxylalkyl) ferrocenes in rocket propellants |
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US031041A US3874957A (en) | 1970-04-07 | 1970-04-07 | Use of 1,1'-bis-(1-glycidoxylalkyl) ferrocenes in rocket propellants |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4391660A (en) * | 1981-09-10 | 1983-07-05 | The United States Of America As Represented By The Secretary Of The Air Force | Copper containing ballistic additives |
US4397700A (en) * | 1982-02-24 | 1983-08-09 | The United States Of America As Represented By The Secretary Of The Navy | Piperazine derivatives of ferrocene |
US5872328A (en) * | 1996-03-06 | 1999-02-16 | Chemische Betriebe Pluto Gmbh | Ferrocene derivatives |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3437634A (en) * | 1964-06-01 | 1969-04-08 | Mc Donnell Douglas Corp | Reactive ferrocene polymers |
US3598850A (en) * | 1969-06-11 | 1971-08-10 | Us Air Force | Ferrocene polyglycols |
-
1970
- 1970-04-07 US US031041A patent/US3874957A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3437634A (en) * | 1964-06-01 | 1969-04-08 | Mc Donnell Douglas Corp | Reactive ferrocene polymers |
US3598850A (en) * | 1969-06-11 | 1971-08-10 | Us Air Force | Ferrocene polyglycols |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4391660A (en) * | 1981-09-10 | 1983-07-05 | The United States Of America As Represented By The Secretary Of The Air Force | Copper containing ballistic additives |
US4397700A (en) * | 1982-02-24 | 1983-08-09 | The United States Of America As Represented By The Secretary Of The Navy | Piperazine derivatives of ferrocene |
US5872328A (en) * | 1996-03-06 | 1999-02-16 | Chemische Betriebe Pluto Gmbh | Ferrocene derivatives |
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