USH448H - Co-nitration of 1,2,4-butanetriol and glycerin - Google Patents
Co-nitration of 1,2,4-butanetriol and glycerin Download PDFInfo
- Publication number
- USH448H USH448H US07/070,758 US7075887A USH448H US H448 H USH448 H US H448H US 7075887 A US7075887 A US 7075887A US H448 H USH448 H US H448H
- Authority
- US
- United States
- Prior art keywords
- butanetriol
- glycerin
- mixture
- acid
- weight percent
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/10—Compositions containing a nitrated organic compound the compound being nitroglycerine
- C06B25/12—Compositions containing a nitrated organic compound the compound being nitroglycerine with other nitrated organic compounds
- C06B25/14—Compositions containing a nitrated organic compound the compound being nitroglycerine with other nitrated organic compounds the other compound being a nitrated aliphatic diol
-
- 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
Definitions
- This invention relates to nitrate esters and more particularly to methods of co-nitrating polyols to produce nitrate ester mixtures.
- 1,2,4-butanetriol trinitrate and nitroglycerin are useful as energetic components in explosives and gun propellants.
- 1,2,4-butanetriol and glycerin are nitrated separately to form 1,2,4-butanetriol trinitrate and nitroglycerin which are then blended together in the desired proportions.
- fume-offs frequently occur during the nitration of 1,2,4-butanetriol alone. It would be desirable to provide a method of reducing or eliminating these problems.
- an object of this invention is to provide a new method of producing mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
- Another object of this invention is to provide a safer method of producing mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
- a further object of this invention is to avoid fume-offs during the preparation of mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
- a binary polyol mixture of from about 40 to about 60 weight percent of 1,2,4-butanetriol with the remainder of the polyol mixture being glycerin;
- 1,2,4-butanetriol HOCH 2 CH(OH)CH 2 CH 2 OH
- glycerin HOCH 2 CH(OH)CH 2 OH
- a mixed acid containing from 30 to 60 weight percent of nitric acid with the remainder being sulfuric acid is used as the nitrating agent.
- a more preferred mixed acid will contain from 38 to 42 weight percent of nitric acid with the remainder being sulfuric acid.
- the amount of mixed acid used will preferably provide an excess of from 30 to 50 percent of nitric acid based on the stoichiometric amount calculated for the complete conversion of 1,2,4-butanetriol and glycerin to 1,2,4-butanetriol trinitrate g and nitroglycerin. More preferably an excess of from 40 to 44 percent of nitric acid is used.
- the polyol mixture is fed into the mixed acid with vigorous agitation (e.g., stirring) of the mixed acid to prevent hot spots. Agitation of the reaction mixture is continued during the nitration step.
- the nitration reaction is exothermic and conventional methods such as rate of polyol feed and external cooling are used to control the reaction temperature.
- the reaction temperature is kept in the range of from 5° C. to 20° C. Below 5° C. certain reactants may freeze and separate from the reaction mixture. Temperatures above 20° C. may result in the decompostion of the products.
- the product 1,2,4-butanetriol trinitrate/nitroglycerin mixture separates as a clear oil from the spent acid phase. There is no stable oil/water emulsion formed. This contrasts with the nitration of glycerin alone in which some stable emulsion of nitroglycerin and water is usually formed.
- the product 1,2,4-butanetriol trinitrate/nitroglycerin oil mixture is washed first with a weak aqueous base and then with water to remove traces of the acids.
- BTTN 1,2,4-butanetriol trinitrate
- NG nitroglycerin
- Example 2 The same as Example 1 except that a binary mixture of 52.07 weight percent of 1,2,4-butanetriol (99.8 percent pure) and 47.93 weight percent of glycerin was pumped into the mixed acid at a rate of 3.3 grams per minute. The change in redox was 49 mv. (A sample of this 1,2,4-butanetriol nitrated by itself had a change of redox of 58 mv.) The 1,2,4-butanetriol trinitrate (BTTN)/nitroglycerin (NG) mixture was separated from the spent acid. The results of the spent acid analysis were:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing an energetic mixture of 1,2,4-butanetroil trinitr and nitroglycerin by forming a polyol mixture of 1,2,4-butanetriol and glycerin, and then nitrating the polyol mixture with a mixture of nitric and sulfuric acids.
Description
This invention relates to nitrate esters and more particularly to methods of co-nitrating polyols to produce nitrate ester mixtures.
Mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin are useful as energetic components in explosives and gun propellants. Normally, 1,2,4-butanetriol and glycerin are nitrated separately to form 1,2,4-butanetriol trinitrate and nitroglycerin which are then blended together in the desired proportions. This requires that one of the nitrate esters be stored while the other is being made. This storage is undesirable because either nitroglycerin or 1,2,4-butanetriol trinitrate is more sensitive to impact than a blended mixture of the two. Moreover, fume-offs frequently occur during the nitration of 1,2,4-butanetriol alone. It would be desirable to provide a method of reducing or eliminating these problems.
Accordingly, an object of this invention is to provide a new method of producing mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
Another object of this invention is to provide a safer method of producing mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
A further object of this invention is to avoid fume-offs during the preparation of mixtures of 1,2,4-butanetriol trinitrate and nitroglycerin.
These and other objects of this invention are accomplished by providing a process for preparing an energetic binary mixture of 1,2,4-butanetriol trinitrate and nitroglycerin by:
a. forming a binary polyol mixture of from about 40 to about 60 weight percent of 1,2,4-butanetriol with the remainder of the polyol mixture being glycerin;
b. nitrating the polyol mixture with a mixed acid of from 30 to 60 weight percent of nitric acid with the remainder of the mixed acid being sulfuric acid; and
c. isolating the product mixture of 1,2,4-butanetriol trinitrate and nitroglycerin.
It is critical that the 1,2,4-butanetriol, HOCH2 CH(OH)CH2 CH2 OH, and glycerin, HOCH2 CH(OH)CH2 OH, starting materials be thoroughly mixed prior to the nitration step. In this way fuming off (of nitric acid), which frequently occurs in the normal nitration of 1,2,4-butanetriol, is avoided. Preferably from about 40 to about 60 and more preferably from 50 to 55 weight percent of 1,2,4-butanetriol is used, with glycerin being the remainder of the polyol mixture.
A mixed acid containing from 30 to 60 weight percent of nitric acid with the remainder being sulfuric acid is used as the nitrating agent. A more preferred mixed acid will contain from 38 to 42 weight percent of nitric acid with the remainder being sulfuric acid.
The amount of mixed acid used will preferably provide an excess of from 30 to 50 percent of nitric acid based on the stoichiometric amount calculated for the complete conversion of 1,2,4-butanetriol and glycerin to 1,2,4-butanetriol trinitrate g and nitroglycerin. More preferably an excess of from 40 to 44 percent of nitric acid is used.
Preferably the polyol mixture is fed into the mixed acid with vigorous agitation (e.g., stirring) of the mixed acid to prevent hot spots. Agitation of the reaction mixture is continued during the nitration step. The nitration reaction is exothermic and conventional methods such as rate of polyol feed and external cooling are used to control the reaction temperature. Preferably the reaction temperature is kept in the range of from 5° C. to 20° C. Below 5° C. certain reactants may freeze and separate from the reaction mixture. Temperatures above 20° C. may result in the decompostion of the products.
The product 1,2,4-butanetriol trinitrate/nitroglycerin mixture separates as a clear oil from the spent acid phase. There is no stable oil/water emulsion formed. This contrasts with the nitration of glycerin alone in which some stable emulsion of nitroglycerin and water is usually formed.
As illustrated in the examples, the product 1,2,4-butanetriol trinitrate/nitroglycerin oil mixture is washed first with a weak aqueous base and then with water to remove traces of the acids.
To more clearly illustrate this invention, the following examples are presented. It should be understood, however, that these examples are presented merely as a means of illustration and are not intended to limit the scope of the invention in any way.
46.6 grams of a binary solution of 53.1 weight percent of 1,2,4-butanetriol (96 percent pure) and 46.9 weight percent of glycerin at 41° C. was pumped into 300 grams of mixed acid (38.1 weight percent of nitric acid and 58.8 weight percent of sulfuric acid) at 15±1° C. This is a 43 percent excess of nitric acid. During the nitration the mixture was agitated with a high-speed, high-shear mixer. During the nitration the change in redox was 80 mv. (A sample of this 1,2,4-butanetriol nitrated by itself had a change in redox of 130 mv.) The nitration mixture was drowned in 1000 grams of 6° C. water with a 18° C. temperature rise. The calculated spent acid analysis was:
______________________________________ % Nitric Acid 11.8 % Sulfuric Acid 71.8 % Oxides 0.5 % Water assuming 1% NG 13.9 and 1% BTTN H.sub.2 O/H.sub.2 SO.sub.4 Mole Ratio 1.05 ______________________________________
The 1,2,4-butanetriol trinitrate (BTTN)/nitroglycerin (NG) mixture at 35° to 40° C. was washed four times with 300 ml of 13 percent sodium carbonate and 3 times with water. Each wash was agitated for 15 minutes with the high-speed, high-shear agitator. The results of the BTTN-NG analysis are:
______________________________________ % BTTN 52.1 % NG 46.9 KI heat test min 18 10 min minimum % water 0.1 % N 17.9 pH Neutral ______________________________________
The same as Example 1 except that a binary mixture of 52.07 weight percent of 1,2,4-butanetriol (99.8 percent pure) and 47.93 weight percent of glycerin was pumped into the mixed acid at a rate of 3.3 grams per minute. The change in redox was 49 mv. (A sample of this 1,2,4-butanetriol nitrated by itself had a change of redox of 58 mv.) The 1,2,4-butanetriol trinitrate (BTTN)/nitroglycerin (NG) mixture was separated from the spent acid. The results of the spent acid analysis were:
______________________________________ % Nitric Acid 9.16 % Sulfuric Acid 75.68 % Oxide 0.64 % Water (calculated) 11.6 H.sub.2 O/H.sub.2 SO.sub.4 Mole Ratio 0.86 ______________________________________
The results of BTTN-NG analysis were:
______________________________________ KI heat test 8.7 min % BTTN 50.9 % NG 49.1 ______________________________________
To those skilled in the art, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that the present invention can be practiced otherwise than as specifically described herein and still be within the scope of the appended claims.
Claims (6)
1. A process for preparing an energetic binary mixture of 1,2,4-butanetriol trinitrate and nitroglycerin comprising:
a. forming a binary polyol mixture consisting essentially of from about 40 to about 60 weight percent of 1,2,4-butanetriol with the remainder of the polyol mixture being glycerin;
b. nitrating the polyol mixture with a mixed acid consisting essentially of from 30 to 60 weight percent of nitric acid with the remainder of the mixed acid being sulfuric acid; and
c. isolating the product mixture of 1,2,4-butanetriol trinitrate and nitroglycerin.
2. The process of claim 1 wherein the binary polyol mixture consists essentially of from 50 to 55 weight percent of 1,2,4-butanetriol with the remainder of the polyol mixture being glycerin.
3. The process of claim 1 wherein the nitration temperature is maintained in the range of from 5° C. to 20° C. during step (b).
4. The process of claim 1 wherein the mixed acid consists essentially of from 38 to 42 weight percent of nitric acid with the remainder of the mixed acid being sulfuric acid.
5. The process of claim 1 wherein the amount of mixed acid used in step (b) provides a 30 to 50 percent excess of nitric acid over the stoichiometric amount calculated for the complete nitration of the 1,2,4-butanetriol and glycerin.
6. The process of claim 5 wherein the amount of mixed acid used in step (b) provides a 40 to 44 percent excess of nitric acid over the stoichiometric amount calculated for the complete nitration of the 1,2,4-butanetriol and glycerin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/070,758 USH448H (en) | 1987-07-06 | 1987-07-06 | Co-nitration of 1,2,4-butanetriol and glycerin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/070,758 USH448H (en) | 1987-07-06 | 1987-07-06 | Co-nitration of 1,2,4-butanetriol and glycerin |
Publications (1)
Publication Number | Publication Date |
---|---|
USH448H true USH448H (en) | 1988-03-01 |
Family
ID=22097213
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/070,758 Abandoned USH448H (en) | 1987-07-06 | 1987-07-06 | Co-nitration of 1,2,4-butanetriol and glycerin |
Country Status (1)
Country | Link |
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US (1) | USH448H (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5482581A (en) * | 1988-08-25 | 1996-01-09 | Ici Explosives Usa Inc. | Low vulnerability propellant plasticizers |
US5520757A (en) * | 1988-08-25 | 1996-05-28 | Ici Explosives Usa Inc. | Low vulnerability propellants |
-
1987
- 1987-07-06 US US07/070,758 patent/USH448H/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5482581A (en) * | 1988-08-25 | 1996-01-09 | Ici Explosives Usa Inc. | Low vulnerability propellant plasticizers |
US5520757A (en) * | 1988-08-25 | 1996-05-28 | Ici Explosives Usa Inc. | Low vulnerability propellants |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNITED STATES OF AMERICA AS REPRESENTED BY THE SEC Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:FARNCOMB, ROBERT E.;CARR, WALTER A.;REEL/FRAME:004735/0177 Effective date: 19870626 |
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STCF | Information on status: patent grant |
Free format text: PATENTED CASE |