GB2181124A - Process for producing high energy materials - Google Patents
Process for producing high energy materials Download PDFInfo
- Publication number
- GB2181124A GB2181124A GB8520345A GB8520345A GB2181124A GB 2181124 A GB2181124 A GB 2181124A GB 8520345 A GB8520345 A GB 8520345A GB 8520345 A GB8520345 A GB 8520345A GB 2181124 A GB2181124 A GB 2181124A
- Authority
- GB
- United Kingdom
- Prior art keywords
- process according
- high energy
- heterocyclic compound
- substituents
- nitrogen oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C203/00—Esters of nitric or nitrous acid
- C07C203/02—Esters of nitric acid
- C07C203/04—Esters of nitric acid having nitrate groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/02—Preparation of esters of nitric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
Abstract
A process for the production of a high energy material involves reacting, in an inert organic solvent, a heterocyclic compound selected from oxirane and oxetane with a nitrogen oxide selected from dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) and, when the nitrogen oxide is N2O4, oxidising the O- nitroso substituent or substituents in the product obtained to O-nitro substituent or substituents. The heterocyclic compounds may be substitued or unsubstituted. In the former case the preferred substituents groups are halogen, alkyl, alkenyl, nitro and epoxy (as in epoxidised polybutadiene). The solvent is preferably a chlorinated alkane.
Description
SPECIFICATION
A process for the production of high energy materials
The present invention relates to a process for the production of high energy materials, to high energy materials produced thereby and to certain novel high energy materials.
At present the manufacture of the group of high energy materials which contain nitrate ( nitro) substituents or the analogous materials which contain a mixture of Nitro substituents generally requires the use of strong mineral acids (especially HNO3/H2SO4 mixtures) and high temperatures. These conditions present the manufacturer of the these materials with a number of problems which he must overcome if the method of production is to meet modern standards of safety. These problems include the control, containment and disposal of a highly dangerous and corrosive reaction mixture (hot mineral acids).
It is one object of the present invention to overcome at least some of the above problems by providing a process for the production of certain high energy materials (especially those which contain Onitro substituents) which proceeds effectively at ambient temperature (0-300C), employs inert organic solvents, and does not require the disposal of strong mineral acids.
Other objects and advantages of the present invention will become apparent from the following description thereof.
According to the present invention a process for the production of a high energy material comprises reacting, in an inert organic solvent, a heterocyclic compound selected from the group oxirane (ethylene oxide) and oxetane with a nitrogen oxide selected from the group dinitrogen tetroxide (N204) and dinitrogen pentoxide (N2O5) and, when the nitrogen oxide is dinitrogen tetroxide, oxidising the Onitroso substituent or substituents in the product obtained to Onitro substituent or substituents.
In the present specification each of the terms oxirane and oxetane encompasses both the unsubstituted compounds and the substituted derivatives of the compounds. In the latter case the heterocyclic ring may be substituted by any substituent group. Preferably however the substituent group is at least one of the following halogen, alkyl, akenyl, nitro and epoxy (as in butadiene diepoxide or the epoxidised form of a polybutadiene), although other groups, such as aldehydo, amino, amido, acyl, carboxylate ester, carboxylic acid, hydroxy, alkoxy, aryl and alkyne, may either additionally or alternatively be present.
The reaction, between heterocyclic compound and nitrogen oxide, is conducted in an inert organic solvent. Any anhydrous organic solvent which does not react with either the starting materials or the reaction products of the present process may be employed. Preferably, however, it should also be possible to either dispose of or recycle the solvent, simply, safely and at little cost. The chlorinated alkanes, dichloromethane, chloroform and carbon tetrachloride, generally meet these criteria and are therefore preferred.
The present process may be conducted at high temperature (up to the boiling point of the solvent) and/or pressure. It is preferred, however, to allow the reaction to proceed at ambient temperature (O-30 C, especially 10-20 C) and pressure.
When the present heterocyclic compounds are reacted with dinitrogen pentoxide the required high energy materials are obtained without further treatment of the reaction mixture. However, when the present heterocyclic compounds are reacted with dinitrogen tetroxide the required high energy materials are only obtained after subsequent oxidation of the resultant nitrnso compounds. This oxidation step may be performed by any oxidising agent that transforms and O-nitroso substituent into an Nitro substituent provided that the agent has no effect on any other part of the nitroso compound (eg does not oxidise a double bond or- hydrolyse a halo substituent). In many cases the preferred oxidising agent is ozone.
Generally the present process proceeds very quickly at ambient temperature and pressure.
In a few cases, however, the process, as described above, may be-rather slow and it may be necessary to increase the rate of reaction.
This may be done by increasing the reaction temperature to above the ambient; alternatively the reaction may be controlled by the presence of a Lewis acid such as aluminium chloride or stannic chloride.
Although some of the products of the present process are known compounds, in a further aspect of the present invention there is provided a novel group of nitrated polymers.
More specifically there is provided a nitrated polybutadiene, especially a hydroxy-terminated polybutadiene, in which between 1% and 25%, especially between 5% and 20%, of the carbon atoms in the polymer are substituted by nitrate (ONO2) groups. These novel materials are liquid rubbers when the polybutadiene starting material (prior to nitration) has a molecular weight between 200 and 10000.
The present process will now be described by way of example only.
Preparation of Dinitrogen Pentoxide (N205) N2Os) may be prepared by the oxidation of dinitrogen tetroxide (N204) with ozone. Because of the thermal instability of N205, during the preparation and subsequent use the temperature should not exceed 30"C and preferably operations are carried out between 0 and 20"C. All operations must be carried out under anhydrous conditions since N205 is readily hydrolysed to nitric acid. For the reactions described here it is convenient to dissolve the
N205 in an inert solvent, such as a chlorinated alkane.
An ozone/oxygen mixture, from a commercially available ozoniser was passed into a glass vessel containing N204. Oxidation occurs in the gas phase and the resulting N2Os is carried in the oxygen stream and trapped in a series of cold traps kept at --20"C to -300C.
Any unreacted N204 is subsequently reacted by resubliming the initial trapped product in an ozonised oxygen stream. The pure, white crystals of N205 can be stored at -78"C for at least 7 days before use without any noticeable decomposition.
Dinitrogen Tetroxide (N2OA) N204 was obtained commercially as a compressed gas and was used in the following examples directly from a cylinder.
Reactions of Nitrogen Oxides with Heterocyclic
Compounds
General Procedures
A. Reaction with N2O5 A solution of N205 in an inert solvent was prepared. The heterocyclic compound, dissolved in the same solvent, was added to the stirred N205 solution in an equimolar amount.
The reaction was immediate and generally carried out at or bellow room temperature in order to minimise the thermal decomposition of
N205 and in some cases to avoid losses of the reacting compound where it's volatility was high. Precautions were taken to avoid hydrolysis of the N205 by atmospheric water vapour. Any excess acidity was removed by stirring with solid sodium hydrogen carbonate and the product was isolated by vaccum distillation of the solvent.
B. Reaction with N204 and subsequent oxidation of the product
A solutuion of N204 was prepared by absorption of the gas into a dry inert solvent and the heterocyclic compound was added in an equimolar amount to this stirred solution.
The reaction mixture was stirred at room temperature for 30 mins and the resultant product (a nitrite-nitrite ester) was oxidised, in situ, with an anhydrous oxidising agent, for example ozone. After removal of any excess acidity with sodium hydrogen carbonate the product was isolated by vacuum distillation of the solvent.
Specific Examples
1. Ethylene Oxide
Ethylene oxide was reacted with N205 using the general procedure (A) described above.
The product was the dinitrate ester of ethylene (O2NOH2C CH2ONOJ. In some runs small amounts of ethylene glycol mononitrate were observed through the reaction of traces of nitric acid with ethylene oxide.
Ethylene oxide has also been reacted with N204 and subsequently oxidised with ozone, general procedure (B) above. The product of this reaction is also the dinitrate ester of ethylene glycol.
2. Propylene oxide
Propylene oxide was reacted with N205 as described in general procedure (A) to yield propylene glycol dinitrate (CH3CH(ONO 2)CH20NO2).
3. Epichlorohydrin
Reaction of epichlorohydrin with N205, general procedure (A), gave 1-chloro-2, 3-propanediol dinitrate (ONO2CH2CH(ONO2)CH2CI).
4. Butadiene Monoepoxide
Butadiene monoepoxide was reacted with
N205 as described above in general procedure (A). The product was 3, 4-butenediol dinitrate, (CH2=CHCH(0N02)CH2ONO2).
5. Butadiene Diepoxide
Butadiene diepoxide was reacted with N205 as described in general procedure (A) except that the nitrogen oxide was added to the epoxide. This reaction gave mainly 1, 2epoxy-3, 4-butanediol dinitrate, although some polymeric products were also produced.
Reaction of 2 moles of N205 with 1 mole of butadiene diepoxide by the same procedure gave erythritol tetranitrate (O2NOCH2CH(ONO 2)CH(ONO2)CH20N02).
6. Epoxidised Polybutadiene
A commercially available hydroxy terminated polybutadiene was epoxidised by known procedures to give partially epoxidised materials where the degree of epoxidation ranged from
10 to 50% of the theoretical maximum. Solutions of these materials were reacted with an amount of N205 equivalent to the degree of epoxidation by the method of general procedure (A). The resulting polymers contained nitrate ester groups. The materials were liquid rubbers.
7. Oxetane
Reaction of oxetane with N205, as described in general procedure (A), gave 1, 3-propanediol dinitrate (O2NO(CHJ3ONO2).
8. 3,3-Dimethyloxetane
Reaction of 3,3-dimethyl oxetane with N205, as described in general procedure (A), gave 2, 2-dimethyl- 1, 3-propanediol dinitrate.
9. 3, 3-Pentamethylene oxetane
Reaction of 3, 3-pentamethyleneoxetane with N205, as described in general procedure (A), gave 2, 2-pentamethylene-1, 3-propanediol dinitrate.
Claims (11)
1. A process for the production of a high energy material comprises reacting, in an inert organic solvent, a heterocyclic compound selected from the group oxirane and oxetane with a nitrogen oxide selected from the group dinitrogen tetroxide and dinitrogen pentoxide and, when the nitrogen oxide is dinitrogen tetroxide, oxidising the O-nitroso substituent or substituents in the product obtained to O-nitro substituent or substituents.
2. A process according to claim 1 wherein the heterocyclic compound is substituted by at least one group selected from halogen, alkyl, alkenyl, nitro and epoxy.
3. A process according to either claim 1 or claim 2 wherein the inert organic solvent comprises dichloromethane, chloroform or carbon tetrachloride.
4. A process according to any one of claims 1 to 3 wherein the O-nitroso substituents are oxidised by treatment with ozone.
5. A process according to any one of claims 1 to 4 wherein the reaction between the heterocyclic compound and the nitrogen oxide is performed in the presence of a Lewis acid.
6. A process according to any one of claims 1 to 5 wherein the heterocyclic compound comprises an epoxidised polybutadiene.
7. A process according to claim 6 wherein the heterocyclic compound comprises an epoxidised hydroxy-terminated polybutadiene.
8. A process according to any one of claims 1 to 5 wherein the heterocyclic compound comprises ethylene oxide, propylene oxide, epichlorohydrin, butadiene monoepoxide, butadiene diepoxide, oxetane, 3, 3-dimethyloxetane or 3, 3-pentamethyleneoxetane.
9. A process for the production of a high energy material according to claim 1 substantially as hereinbefore described with particular reference to any one of Examples 1 to 10.
10. A high energy material whenever prepared by a process according to any one of claims 1 to 9.
11. A high energy polybutadiene material whenever prepared by a process according to either claim 6 or claim 7.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8520345A GB2181124B (en) | 1982-07-15 | 1985-08-14 | Process for producing high energy materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8220082 | 1982-07-15 | ||
GB8520345A GB2181124B (en) | 1982-07-15 | 1985-08-14 | Process for producing high energy materials |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2181124A true GB2181124A (en) | 1987-04-15 |
GB2181124B GB2181124B (en) | 1987-10-14 |
Family
ID=26283314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8520345A Expired GB2181124B (en) | 1982-07-15 | 1985-08-14 | Process for producing high energy materials |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2181124B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998009937A1 (en) * | 1996-09-05 | 1998-03-12 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Process for the production of dinitrate esters |
GB2331749A (en) * | 1996-09-05 | 1999-06-02 | Secr Defence Brit | Process for the production of dinitrate esters |
WO2000058261A1 (en) * | 1999-03-03 | 2000-10-05 | The Secretary Of State For Defence | Solid nitrating reagent |
WO2001002336A1 (en) * | 1999-07-03 | 2001-01-11 | Qinetiq Limited | Process for the production of glycerol dinitrates |
-
1985
- 1985-08-14 GB GB8520345A patent/GB2181124B/en not_active Expired
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998009937A1 (en) * | 1996-09-05 | 1998-03-12 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Process for the production of dinitrate esters |
GB2331749A (en) * | 1996-09-05 | 1999-06-02 | Secr Defence Brit | Process for the production of dinitrate esters |
US6072071A (en) * | 1996-09-05 | 2000-06-06 | The Secretary Of State For Defence In Her Britannic Majesty's Goverment Of The United Kingdom Of Great Britain And Northern Ireland | Process for the production of dinitrate esters |
GB2331749B (en) * | 1996-09-05 | 2000-06-28 | Secr Defence Brit | Process for the production of dinitrate esters |
WO2000058261A1 (en) * | 1999-03-03 | 2000-10-05 | The Secretary Of State For Defence | Solid nitrating reagent |
WO2001002336A1 (en) * | 1999-07-03 | 2001-01-11 | Qinetiq Limited | Process for the production of glycerol dinitrates |
Also Published As
Publication number | Publication date |
---|---|
GB2181124B (en) | 1987-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4820859A (en) | Process for the production of high energy material | |
US5136062A (en) | Preparation of epoxy nitrates | |
CA1328112C (en) | Preparation of epoxy nitrates | |
EP0274213B1 (en) | Process for the preparation of alkyl azide-substituted, hydroxy-terminated polyethers | |
GB2181124A (en) | Process for producing high energy materials | |
Freeman | The Reactions of Certain Oxidized Nitrogen Compounds with Perchloryl Fluoride1 | |
JPS58172387A (en) | Manufacture of 2,2-dicyclohexenylpropane diepoxide | |
Golding et al. | Preparation of di-and polynitrates by ring-opening nitration of oxetanes by dinitrogen pentoxide (N2O5) | |
GB2181139A (en) | Nitrated polybutadiene | |
JP2661903B2 (en) | Manufacturing method of high energy materials | |
US4985584A (en) | Process for the production of high energy materials | |
EP0466942B1 (en) | Composition comprising epoxy compounds having hydroxyl group and process for producing the same | |
US6177033B1 (en) | Nitration of organics in carbon dioxide | |
US3058994A (en) | Process for the production of nitratoalkyl oxetanes | |
US5214166A (en) | Method of synthesizing nitrato alkyl oxetanes | |
US3476776A (en) | Process for the manufacture of alkane epoxides | |
US3250791A (en) | Tetracyanoethylene oxide and process for preparing same | |
GB2008593A (en) | Process for the preparation of epoxides | |
JPS6338029B2 (en) | ||
US4683086A (en) | Azido derivatives of pentaerythritol | |
US5268493A (en) | Method of producing olefin oxide | |
EP0293555A2 (en) | Azide-terminated azido compound | |
US3278554A (en) | Esters containing more than one oxetane group | |
US3341556A (en) | Process for the production of propylene oxide | |
US4012423A (en) | Process for the production of epoxides |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
727 | Application made for amendment of specification (sect. 27/1977) | ||
727A | Application for amendment of specification now open to opposition (sect. 27/1977) | ||
727B | Case decided by the comptroller ** specification amended (sect. 27/1977) | ||
SP | Amendment (slips) printed | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19970712 |