US3388141A - Di-schiff bases of hydroxyl substituted diamines and beta-diketones, derivatives, and metal chelates thereof - Google Patents
Di-schiff bases of hydroxyl substituted diamines and beta-diketones, derivatives, and metal chelates thereof Download PDFInfo
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- US3388141A US3388141A US493216A US49321665A US3388141A US 3388141 A US3388141 A US 3388141A US 493216 A US493216 A US 493216A US 49321665 A US49321665 A US 49321665A US 3388141 A US3388141 A US 3388141A
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- 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
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- This invention relates to new chelate complexes and to their preparation and use as a means of modifying the burning rate properties of solid propellant compositions.
- Liquid, curable, polymeric materials are used in the rocket arts as binders to prepare propellant fuels therewith.
- the liquid, curable polymeric materials are blended with the other ingredients of the proposed fuel composition which includes a curing agent for the liquid polymers, oxidizers, fillers and burning rate modifiers and the resulting composition is then subjected to the necessary cure conditions which will cause the liquid polymer to react with the curing agent to form a solid fuel matrix comprising the cured polymer and the various other ingredients of that fuel randomly dispersed therein.
- An object of the present invention is to provide monomeric polymerizable chelates which may be used to modify the burning rate properties of solid propellant compositions made therewith.
- Another object of this invention is to provide means for modifying the burning rate properties of polymeric propellant binder materials by chemically incorporating monomeric chelate materials in the polymeric binder materials.
- a further object is to provide novel and useful intermediates for preparing monomeric polymerizable chelates useful as burning rate modifiers in solid propellant compositions.
- Still another object of this invention is to provide novel chelate containing polymers.
- the burning rate properties of a propellant composition or matrix can be readily and reproducibly regulated if the polymeric binder used in the fabrication of the matrix is formed, in part, from one or more monomeric, polymerizable chelates having the structure where R and R each represent either hydrogen or a lower alkyl group, R represents either hydrogen, acryloyl, methacrylolyl, vinyl or isopropenyl, R and R each represent a lower alkyl group, and M represents a heavy metal such as iron, nickel, cobalt, copper, cadmium, zinc, lead and manganese.
- the chelate moieties act as the burning rate modifiers for the propellant composition and the desired burning rate characteristics can be readily and reproducibly imparted to the propellant matrix by regulating the amount and type of chelate incorporated in the polymeric binder. Being an integral component of the liquid polymer binder, the chelate burning rate modifiers of the present invention are readily dispersed, uniformly, throughout the propellant matrix.
- polymerizable monomeric chelates which are usefully employed as burning rate controlling components of solid propellant fuels according to the present invention are prepared by a three-step process according to Equations 1, 2 and 3, shown below.
- a fi-hydroxyl-LB-diamine is first reacted with 2 moles of a 1,3-diketone in a solvent medium such as ethanol to form a di-Schifi base R CH(NH )CH(OH)CH(NH )R (Equation '1) in which R and R each represent either hydrogen or a lower alkyl group, and R and R each represent a lower alkyl group.
- the di-Schitf base, sodium hydroxide, and sodium acetate is then dissolved in boiling water and reacted with a soluble salt of a heavy metal.
- R4 R5 is 0 .Acrylyl chloride in triethylamine HO M Acrylic anhydride N O m
- the extreme insolnbility of this class of metal chelates in water and in organic solvents of all types necessitates the conduction of the esterification reaction under heterogeneous conditions.
- the polymerizable, monomeric chelates disclosed above are copolymerized with one or more of the monomeric materials customarily employed to form such binder materials.
- the monomeric materials include diene and vinyl type monomers such as butadiene, acrylic acid and methacrylic acid.
- the polymerization reaction may be carried out in bulk or in solution using either free radical or ionic type initiators such as azobisisobutyronitrile.
- butadiene/acrylic acid/chelate system is being polymerized the less reactive member, butadiene, is added all at once initially and the more reactive members of the system, acrylic acid and the chelate are added intermittently during the course of the reaction to maintain the ratio of monomers needed to produce a polymer having the desired monomer content.
- the chclate is a solid it may be added to the polymerization system when dissolved in an organic solvent such as benzene.
- the molecular weight of the resulting polymer can be regulated with a chain transfer agent such as t-dodecylmercaptan.
- a chain transfer agent such as t-dodecylmercaptan.
- the polymers are readily recovered from the unreacted monomeric material either by evaporating the more volatile monomers or by washing the polymers.
- Example 1 400.4 grams (4.0 moles) of 2,4-pentanedione in 500 milliliters of benzene was charged into a 2-liter threenecked fiask which was equipped with a stirrer and a condenser and a Dean-Stark trap for removal of water. 180.2 grams (20 moles) of 2-hydroxy-L3-propylenediamine was added dropwise while stirring during 20 minutes to the reaction flask. After the initial reaction had subsided, the admixture was heated under reflux for 4 hours. During the reflux period the theoretical amount of water (72 grams) was collected in the water trap.
- Analogous chelate product of othe. metals may be prepared by substituting for the iron sulfate-751 0 in the above reaction other metal salts, such as, for example, nickel chloride-6H O and the respective acetate salts of cobalt, copper, cadmium, zinc, lead, and manganese.
- other metal salts such as, for example, nickel chloride-6H O and the respective acetate salts of cobalt, copper, cadmium, zinc, lead, and manganese.
- the acrylate ester of the iron chelate product is prepared by reacting the iron chelate product with acrylic anhydride.
- a curable, polymeric binder material is prepared by copolymerizing the iron chelate product or the acrylate ester of such product with vinyl compounds such as butadiene and acrylic acid and recovering the polymeric product.
- composition of matter having the structure -N OH in which R and R each represent substituents selected from the group consisting of hydrogen atoms and lower alkyl groups, and R and R each represent a lower alkyl group.
- composition of matter according to claim 1 in which R.,, and R each represent a methyl group.
- R and R each represent a substituent selected from the group consisting of hydrogen atoms and lower alkyl groups
- R represents a substituent selected from the group consisting of hydrogen, acryloyl, methacryloyl, vinyl, and isopropenyl groups, R; and R each represents a lower alkyl group, and M represents a heavy metal.
- composition of matter according to claim 4 in which R and R represent a methyl group.
- M is heavy metal selected from the group consisting of iron, nickel, cobalt, copper, cadmium, zinc, lead, and manganese.
- composition of matter according to claim 4 in which R is an acryloyl group.
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Description
United States Patent 3,388,141 DI-SCHIFF BASES OF HYDROXYL SUBSTITUTED DIAMINES AND B-DKKETONES, DERIVATIVES, AND METAL CHELATES THEREOF Morris B. Berenbaum, Levittowu, Pa., assignor to Thiokol Chemical Corporation, Bristol, Pa., a corporation of Delaware No Drawing. Filed Oct. 5, 1965, Ser. No. 493,216 13 Claims. (Cl. 260439) ABSTRACT OF THE DISCLOSURE The di-Schiff base of a fl-hydroxy-1,3-diamine and a 1,3-diketone are capable of chelating a large number of heavy metal ions. These metal chelates function as burning rate modifiers when incorporated in propellant compositions.
This invention relates to new chelate complexes and to their preparation and use as a means of modifying the burning rate properties of solid propellant compositions.
Liquid, curable, polymeric materials are used in the rocket arts as binders to prepare propellant fuels therewith. The liquid, curable polymeric materials are blended with the other ingredients of the proposed fuel composition which includes a curing agent for the liquid polymers, oxidizers, fillers and burning rate modifiers and the resulting composition is then subjected to the necessary cure conditions which will cause the liquid polymer to react with the curing agent to form a solid fuel matrix comprising the cured polymer and the various other ingredients of that fuel randomly dispersed therein. It is essential that the various components of the solid fuel system be evenly distributed to avoid imparting erratic firing properties to the fuel matrix. Because of the relatively viscous nature of the uncured systems and the relatively large sized batches of the systems usually prepared at one time on a commercial basis it is very dificult, if not impossible, to readily obtain a uniform dispersion of the components throughout the system.
An object of the present invention is to provide monomeric polymerizable chelates which may be used to modify the burning rate properties of solid propellant compositions made therewith.
Another object of this invention is to provide means for modifying the burning rate properties of polymeric propellant binder materials by chemically incorporating monomeric chelate materials in the polymeric binder materials.
A further object is to provide novel and useful intermediates for preparing monomeric polymerizable chelates useful as burning rate modifiers in solid propellant compositions.
Still another object of this invention is to provide novel chelate containing polymers.
It has been unexpectedly found, according to the present invention that the burning rate properties of a propellant composition or matrix can be readily and reproducibly regulated if the polymeric binder used in the fabrication of the matrix is formed, in part, from one or more monomeric, polymerizable chelates having the structure where R and R each represent either hydrogen or a lower alkyl group, R represents either hydrogen, acryloyl, methacrylolyl, vinyl or isopropenyl, R and R each represent a lower alkyl group, and M represents a heavy metal such as iron, nickel, cobalt, copper, cadmium, zinc, lead and manganese. The chelate moieties act as the burning rate modifiers for the propellant composition and the desired burning rate characteristics can be readily and reproducibly imparted to the propellant matrix by regulating the amount and type of chelate incorporated in the polymeric binder. Being an integral component of the liquid polymer binder, the chelate burning rate modifiers of the present invention are readily dispersed, uniformly, throughout the propellant matrix.
The polymerizable monomeric chelates which are usefully employed as burning rate controlling components of solid propellant fuels according to the present invention are prepared by a three-step process according to Equations 1, 2 and 3, shown below.
A fi-hydroxyl-LB-diamine is first reacted with 2 moles of a 1,3-diketone in a solvent medium such as ethanol to form a di-Schifi base R CH(NH )CH(OH)CH(NH )R (Equation '1) in which R and R each represent either hydrogen or a lower alkyl group, and R and R each represent a lower alkyl group.
The di-Schitf base, sodium hydroxide, and sodium acetate is then dissolved in boiling water and reacted with a soluble salt of a heavy metal.
(Equation 2) 11I lii,388,l41
3 The chelate thus produced is then further esterified to form an acrylic ester thereof through its reaction with acrylyl chloride in triethylamine or acrylic anhydride:
R4 R5 is 0 .Acrylyl chloride in triethylamine HO M Acrylic anhydride N O m The extreme insolnbility of this class of metal chelates in water and in organic solvents of all types necessitates the conduction of the esterification reaction under heterogeneous conditions.
In preparing the curable, polymeric binder materials according to the present invention the polymerizable, monomeric chelates disclosed above are copolymerized with one or more of the monomeric materials customarily employed to form such binder materials. The monomeric materials include diene and vinyl type monomers such as butadiene, acrylic acid and methacrylic acid. The polymerization reaction may be carried out in bulk or in solution using either free radical or ionic type initiators such as azobisisobutyronitrile. Where a butadiene/acrylic acid/chelate system is being polymerized the less reactive member, butadiene, is added all at once initially and the more reactive members of the system, acrylic acid and the chelate are added intermittently during the course of the reaction to maintain the ratio of monomers needed to produce a polymer having the desired monomer content. Where the chclate is a solid it may be added to the polymerization system when dissolved in an organic solvent such as benzene.
The molecular weight of the resulting polymer, moreover, can be regulated with a chain transfer agent such as t-dodecylmercaptan. By using the proper ratio of monomers to chain transfer agents, liquid polymers of predetermined viscosities can be obtained. Liquid polymers are preferred because of the relative ease of blending them with the other components of the fuel system.
At the termination of the reaction the polymers are readily recovered from the unreacted monomeric material either by evaporating the more volatile monomers or by washing the polymers.
The following example is merely illustrative of the present invention and is not intended as a limitation upon the scope thereof.
Example 1 400.4 grams (4.0 moles) of 2,4-pentanedione in 500 milliliters of benzene was charged into a 2-liter threenecked fiask which was equipped with a stirrer and a condenser and a Dean-Stark trap for removal of water. 180.2 grams (20 moles) of 2-hydroxy-L3-propylenediamine was added dropwise while stirring during 20 minutes to the reaction flask. After the initial reaction had subsided, the admixture was heated under reflux for 4 hours. During the reflux period the theoretical amount of water (72 grams) was collected in the water trap. On cooling the admixture tan crystals of bis-N,N'-di(2,4- pentanedionyl)-2-hydroXy-1,3-propylene diamine product was formed. The product was recovered by filtration, tol- 75 lowed by recrystallization from benzene. The yield of product was 480 grams. The melting point of the product was l04 to l05.5 C. Elemental analysis of the product showed 11.37% nitrogen as compared with the calculated value for C H O N of 11.02% nitrogen. The bis-N,N'-di(2,4-pentanedionyl)-2-hydroxy-1,3 propylene product was dried and ground to a fine powder. This finely ground product, 15.5 grams of sodium hydroxide and 2 grams of sodium acetate were dissolved in 600 ml. of boiling water. 55.6 grams of iron sulfate-7H O was then added while stirring until the admixture became a paste. The mass was covered with /2 inch of water and allowed to stand for about 20 minutes. The mother liquor was then removed from the mass by means of a centrifuge leaving behind a hard cake. This cake was dried overnight under vacuum at 58 C. to yield bis-N,N- di(2,4 pentanedionyl)-2-hydroxy1,3-propylene diamine iron chelate as a light brown, pyrophoric solid which burned to red iron oxide upon contact with air.
Analogous chelate product of othe. metals may be prepared by substituting for the iron sulfate-751 0 in the above reaction other metal salts, such as, for example, nickel chloride-6H O and the respective acetate salts of cobalt, copper, cadmium, zinc, lead, and manganese.
The acrylate ester of the iron chelate product is prepared by reacting the iron chelate product with acrylic anhydride. A curable, polymeric binder material is prepared by copolymerizing the iron chelate product or the acrylate ester of such product with vinyl compounds such as butadiene and acrylic acid and recovering the polymeric product.
I claim:
.1. A composition of matter having the structure -N OH in which R and R each represent substituents selected from the group consisting of hydrogen atoms and lower alkyl groups, and R and R each represent a lower alkyl group.
2. A composition of matter according to claim 1, in which R.,, and R each represent a methyl group.
3. A composition of matter according to claim 1, in which R; and R each represent hydrogen.
4. A composition of matter having the structure in which R and R each represent a substituent selected from the group consisting of hydrogen atoms and lower alkyl groups, R represents a substituent selected from the group consisting of hydrogen, acryloyl, methacryloyl, vinyl, and isopropenyl groups, R; and R each represents a lower alkyl group, and M represents a heavy metal.
5. A composition of matter according to claim 4, in which R and R represent a methyl group.
6. A composition of matter according to claim 4, in which R and R each represent hydrogen. 1
7. A composition of matter according to claim 4, in which M is heavy metal selected from the group consisting of iron, nickel, cobalt, copper, cadmium, zinc, lead, and manganese.
8. A composition of matter according to claim 7, in which M is iron.
9. A composition of matter according to claim 4, in which R is hydrogen.
10. A composition of matter according to claim 4, in which R is an acryloyl group.
11. A composition of matter according to claim 4, in which R is a methacryloyl group.
12. A composition of matter according to claim 4, in which R is a vinyl group.
13. A composition of matter according to claim 4, in which R is an isopropenyl group.
6 References Cited UNITED STATES PATENTS 4/ 1966 Berenbaum 260429 OTHER REFERENCES Holm, J. Am. Chem. Soc. 82 (1961), pp. 5632-5636.
HELEN M. MCCARTHY, Primary Examiner.
TOBIAS E. LEVOW, Examiner.
A. P. DEMERS, Assistant Examiner.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US493216A US3388141A (en) | 1965-10-05 | 1965-10-05 | Di-schiff bases of hydroxyl substituted diamines and beta-diketones, derivatives, and metal chelates thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| US493216A US3388141A (en) | 1965-10-05 | 1965-10-05 | Di-schiff bases of hydroxyl substituted diamines and beta-diketones, derivatives, and metal chelates thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492176A (en) * | 1968-09-11 | 1970-01-27 | T O Paine | Ammonium perchlorate composite propellant containing an organic transitional metal chelate catalytic additive |
| US3895041A (en) * | 1972-03-20 | 1975-07-15 | Ciba Geigy Corp | Metallised pigments |
| US3963708A (en) * | 1974-07-31 | 1976-06-15 | Ciba-Geigy Corporation | Bis-azomethine metal complex colorants from hydroxycoumarin derivatives or hydroxychromone derivatives |
| US4136254A (en) * | 1976-06-17 | 1979-01-23 | Schering Corporation | Process of selectively blocking amino functions in aminoglycosides using transition metal salts and intermediates used thereby |
| US4184034A (en) * | 1978-01-26 | 1980-01-15 | General Electric Company | Manganese benzoin-imine catalysts and process of preparing polyphenylene ethers using said compounds as catalysts |
| US4260437A (en) * | 1979-05-04 | 1981-04-07 | United Technologies Corporation | Stabilizers for solid propellant binders |
| US4337335A (en) * | 1978-05-18 | 1982-06-29 | Schering Corporation | Transition metal salt complexes of polyamino organic compounds |
| EP0373513A3 (en) * | 1988-12-12 | 1991-03-20 | Air Products And Chemicals, Inc. | Fluorinated beta-ketoimines and beta-ketoiminato metal complexes |
| US5028724A (en) * | 1990-03-30 | 1991-07-02 | Air Products And Chemicals, Inc. | Synthesis of volatile fluorinated and non-fluorinated metal-beta-ketonate and metal-beta-ketoiminato complexes |
| EP0446772A1 (en) * | 1990-03-12 | 1991-09-18 | Air Products And Chemicals, Inc. | Fluorinated beta-ketoiminato metal complexes |
| US6620971B2 (en) * | 2001-01-30 | 2003-09-16 | Samsung Electronics Co., Ltd. | Asymmetric β-ketoiminate ligand compound, preparation method thereof, and organometal percursor comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248410A (en) * | 1962-10-29 | 1966-04-26 | Thiokol Chemical Corp | Chelate burning rate modifiers |
-
1965
- 1965-10-05 US US493216A patent/US3388141A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248410A (en) * | 1962-10-29 | 1966-04-26 | Thiokol Chemical Corp | Chelate burning rate modifiers |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492176A (en) * | 1968-09-11 | 1970-01-27 | T O Paine | Ammonium perchlorate composite propellant containing an organic transitional metal chelate catalytic additive |
| US3895041A (en) * | 1972-03-20 | 1975-07-15 | Ciba Geigy Corp | Metallised pigments |
| US3963708A (en) * | 1974-07-31 | 1976-06-15 | Ciba-Geigy Corporation | Bis-azomethine metal complex colorants from hydroxycoumarin derivatives or hydroxychromone derivatives |
| US4136254A (en) * | 1976-06-17 | 1979-01-23 | Schering Corporation | Process of selectively blocking amino functions in aminoglycosides using transition metal salts and intermediates used thereby |
| US4184034A (en) * | 1978-01-26 | 1980-01-15 | General Electric Company | Manganese benzoin-imine catalysts and process of preparing polyphenylene ethers using said compounds as catalysts |
| US4337335A (en) * | 1978-05-18 | 1982-06-29 | Schering Corporation | Transition metal salt complexes of polyamino organic compounds |
| US4260437A (en) * | 1979-05-04 | 1981-04-07 | United Technologies Corporation | Stabilizers for solid propellant binders |
| EP0373513A3 (en) * | 1988-12-12 | 1991-03-20 | Air Products And Chemicals, Inc. | Fluorinated beta-ketoimines and beta-ketoiminato metal complexes |
| EP0446772A1 (en) * | 1990-03-12 | 1991-09-18 | Air Products And Chemicals, Inc. | Fluorinated beta-ketoiminato metal complexes |
| US5028724A (en) * | 1990-03-30 | 1991-07-02 | Air Products And Chemicals, Inc. | Synthesis of volatile fluorinated and non-fluorinated metal-beta-ketonate and metal-beta-ketoiminato complexes |
| US6620971B2 (en) * | 2001-01-30 | 2003-09-16 | Samsung Electronics Co., Ltd. | Asymmetric β-ketoiminate ligand compound, preparation method thereof, and organometal percursor comprising the same |
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