CN1257884C - Trihydroxymethyl hexane trinitrate and its making method - Google Patents
Trihydroxymethyl hexane trinitrate and its making method Download PDFInfo
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- CN1257884C CN1257884C CN 200310123606 CN200310123606A CN1257884C CN 1257884 C CN1257884 C CN 1257884C CN 200310123606 CN200310123606 CN 200310123606 CN 200310123606 A CN200310123606 A CN 200310123606A CN 1257884 C CN1257884 C CN 1257884C
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- trimethylolhexane
- trinitrate
- nitric acid
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Abstract
The present invention relates to trihydroxymethyl hexane trinitrate and a preparation method thereof. The trihydroxymethyl hexane trinitrate can be used for pharmacy and be used as plasticiser and a component of energetic materials, and the trihydroxymethyl hexane trinitrate is an organic intermediate with wide application. The trihydroxymethyl hexane trinitrate has a structural formula of C9H17O9N3 and has a chemical structural formula that trihydroxymethyl hexane is used as a raw material, and the trihydroxymethyl hexane trinitrate is prepared by an esterification reaction under the function of a nitrating agent. The nitrating agent is mixing nitric and sulfuric acid which comprises concentrated nitric acid of 98%, anhydrous nitric acid, concentrated nitric acid and concentrated sulfuric acid, wherein a mass ratio range of nitric acid, sulfuric acid and water is 5 to 25: 90 to 60: 5 to 15; or the mixing nitric and sulfuric acid which comprises the concentrated nitric acid and fuming sulphuric acid is used as the nitrating agent, and a mass ratio range of the nitric acid and the sulfuric acid is 30 to 40: 70 to 60. The reaction temperature is from -5 to 30 DEG C, the reaction time is 0.5 to 7 hours, the mole ratio of trimethylolhexane and the nitric acid is 1: 4 to 30, and urea is used as a catalyst and has the dosage of 1 to 10%.
Description
Technical field
The invention belongs to and a kind ofly prepare the method for nitric ether, be specifically related to Trimethylolhexane trinitrate and preparation method thereof by polyvalent alcohol.
Background technology
Nitroglycerine is a kind of good solvent of widely used nitro-cotton, be used in the double-base propellant in a large number, but nitroglycerine is produced danger, and volatility is bigger, and the trend of moving to the outside from double-base powder inside is arranged, and the intensity of medicine body is reduced.The nitroglycerine double-base powder adopts solvent process production usually, and product storage life is short.
In order to seek the substitute of nitroglycerine, carried out number of research projects both at home and abroad.Developed a kind of trimethylolethane trimethacrylate nitric ether (TMETN) end of the sixties, and made and contain trimethylolethane trimethacrylate nitric ether propelling charge.The trimethylolethane trimethacrylate nitric ether is a kind of energetic plasticiser, it and nitroglycerine structural similitude, and than little many of nitroglycerine, though its impact sensitivity is lower than nitroglycerine, it is not good enough that the insensitiveness performance still shows, at present domestic only small-scale production yet for toxicity.
Trimethylolhexane by enanthaldehyde preparation belongs to polyalcohols, can be used for the lubricating oil field by the trihydroxymethylhexatriacrylate triacrylate of Trimethylolhexane production.Through online information retrieval both at home and abroad, still find no the relevant report for preparing the Trimethylolhexane trinitrate by Trimethylolhexane.
Summary of the invention
The technical problem that the present invention mainly solves is to adopt Trimethylolhexane to prepare the Trimethylolhexane trinitrate.Trimethylolhexane trinitrate insensitiveness performance is good than the trimethylolethane trimethacrylate nitric ether, and dissolving soluble cotton ability is strong, and plasticization effect is good.
Trimethylolhexane trinitrate of the present invention is to be raw material with the Trimethylolhexane, carries out esterification and gets.
Its molecular formula is C
9H
17O
9N
3, chemical structural formula is:
The preparation method of Trimethylolhexane trinitrate of the present invention is: by Trimethylolhexane as raw material, synthesizing trimethylol hexane trinitrate under the effect of nitrating agent, earlier nitrating agent is added in the reactor, again Trimethylolhexane is added in batches, control reaction temperature is-5～30 ℃, and the reaction times is 0.5～7 hour, after reaction is finished, collect resultant from reaction mixture, resultant is the Trimethylolhexane trinitrate.
Above-mentioned nitrating agent is the nitric-sulfuric acid of concentrated nitric acid, anhydrous nitric acid, concentrated nitric acid and the vitriol oil or concentrated nitric acid and oleum composition.The mol ratio of Trimethylolhexane and nitric acid is 1: 4～30; The mass ratio of nitric acid, sulfuric acid and water is 5～25: 90～60 in the nitric-sulfuric acid nitrating agent that the concentrated nitric acid and the vitriol oil are formed: 5～15; Nitric acid and vitriolic mass ratio are 30～40: 70～60 in the nitric-sulfuric acid nitrating agent that concentrated nitric acid and oleum are formed.
Its chemical equation is:
Add urea during synthesizing trimethylol hexane trinitrate as catalyzer, earlier nitrating agent is added in the reactor during reaction, again catalyzer is added.The add-on of above-mentioned catalyzer is 1～10% of Trimethylolhexane by mass percentage.
Above-mentioned esterification reaction temperature is 0～15 ℃, and the nitrated time is 0.5～5 hour, and the mol ratio of Trimethylolhexane and nitric acid is 1: 7～25.
According to synthetic Trimethylolhexane trinitrate of the present invention, detect through Chinese science research institute Shanxi Province's coal chemistry institute, its physicochemical property parameter is as follows:
(1) fusing point is 29～30 ℃;
(2) solubility property: can be dissolved in ethanol, chloroform, the acetone;
(3) refractive index is 1.4876 when being 30 ℃;
(4) ownership of the characteristic peak of infrared spectra (KBr) is: 1641.31cm
-1Be NO
2The asymmetrical stretching vibration peak, this peak is strong and wide, 1282.57cm
-1Be the symmetrical stretching vibration characteristic peak, this peak is strong and wide, 993.2cm
-1Be the stretching vibration of C-O, this peak is strong and wide, 756cm
-1The place is NO
2The swing peak, 703cm
-1NO appears
2Crooked peak, 588cm
-1Be NO
2Wave peak, 2960.53cm
-1, 2933.53cm
-1, 2871.81cm
-1CH appears
3, CH
2The stretching vibration absorption peak;
(5)
1H NMR (uses CDCl
3Make solvent), be methylene peak at δ 4.45ppm place, δ 0.89ppm place is the methyl peak, δ 1.29ppm place is the methylene peak that links to each other with nitro;
(6) ultimate analysis measured value C:34.72%, H:6.10%, O:46.3%, N:13.50%.
The raw material of above-mentioned synthesizing trimethylol hexane trinitrate is a Trimethylolhexane, and it is that raw material is made with enanthaldehyde and formaldehyde.
Enanthaldehyde is a by product of producing Ni Long11, and 1 ton of Ni Long11 of every production just obtains about 1 ton of enanthaldehyde, obtains large batch of enanthaldehyde when producing Ni Long11 in enormous quantities, therefore, and the abundant raw material of synthesizing trimethylol hexane trinitrate, convenient sources.If enanthaldehyde is directly used in sale, cheap, and find no sale, after enanthaldehyde is used to produce the raw material of Trimethylolhexane trinitrate, not only enlarge its purposes, and improved the economic benefit that Ni Long11 is produced greatly.
The Trimethylolhexane trinitrate of the present invention's preparation is compared with the trimethylolethane trimethacrylate nitric ether, many four carbon atoms, has long carbochain, its stability is more much better than trimethylolethane trimethacrylate nitric ether (TMETN), and the growth of carbochain, make the synthetic polyol ester have better oilness, increased the snappiness of molecule itself, its plasticising performance is improved greatly.Compare from the performance of each side such as stability, plasticising performance, volatility, the Trimethylolhexane trinitrate all is better than nitroglycerine and trimethylolethane trimethacrylate nitric ether, therefore, can be used as the ideal substitute of nitroglycerine.
The Trimethylolhexane trinitrate is a kind of broad-spectrum organic intermediate, can be used for pharmacy and uses as the component of softening agent and energetic material.
Below come by some examples that the invention will be further described, in an embodiment, the yield of Trimethylolhexane trinitrate is defined as:
Embodiment
Embodiment 1
The nitrating agent of 98% nitric acid is added in the reactor, under well-stirred condition, the raw material Trimethylolhexane is added in the reactor in batches, the mol ratio of Trimethylolhexane and nitric acid is 1: 20.After reinforced the finishing, continue reaction, temperature is controlled at 0 ℃～15 ℃ in the reaction process, and the time is 0.5～3 hour.After reaction finishes, there is a large amount of crystallizations to occur in the reactor bottom, after filtration, be washed to washing lotion and show neutral, dry, the resultant of collecting from reaction mixture is a white crystals, through infrared spectra, nucleus magnetic resonance and ultimate analysis, prove that the crystallization of white is product Trimethylolhexane trinitrate.The yield of resultant Trimethylolhexane trinitrate can reach 86.2%.
Embodiment 2
Add the nitrating agent and the catalyzer of 98% nitric acid in the reactor successively, under well-stirred condition, add the raw material Trimethylolhexane in the reactor in batches, the mol ratio of Trimethylolhexane and nitric acid is 1: 10, catalyzer is a urea, add-on is 3%～8% of Trimethylolhexane by mass percentage.After reinforced the finishing, continue reaction, temperature is controlled at 5 ℃～25 ℃ in the reaction process, and the time is 1～4 hour.After reaction finishes, there is a large amount of crystallizations to occur in the reactor bottom, after filtration, be washed to washing lotion and show neutral, dry, the resultant of collecting from reaction mixture is a white crystals, through infrared spectra, nucleus magnetic resonance and ultimate analysis, prove that the crystallization of white is product Trimethylolhexane trinitrate.The yield of resultant Trimethylolhexane trinitrate can reach 98.4%.
Embodiment 3
The nitrating agent of anhydrous nitric acid is added in the reactor, under well-stirred condition, the raw material Trimethylolhexane is added in the reactor in batches, the mol ratio of Trimethylolhexane and nitric acid is 1: 25.After reinforced the finishing, continue reaction, temperature is controlled at 10 ℃～20 ℃ in the reaction process, and the time is 2～5 hours.After reaction finishes, there is a large amount of crystallizations to occur in the reactor bottom, after filtration, be washed to washing lotion and show neutral, dry, the resultant of collecting from reaction mixture is a white crystals, through infrared spectra, nucleus magnetic resonance and ultimate analysis, prove that the crystallization of white is product Trimethylolhexane trinitrate.The yield of resultant Trimethylolhexane trinitrate can reach 88.2%.
Embodiment 4
The nitric-sulfuric acid of 98% nitric acid and 98% sulfuric acid composition is added in the reactor as nitrating agent, under well-stirred condition, add the raw material Trimethylolhexane in the reactor in batches, the mol ratio of Trimethylolhexane and nitric acid is 1: 15, the mass ratio of nitric acid, sulfuric acid and water is 5～25: 90～60: 5～15, after reinforced the finishing, continue reaction, temperature is controlled at 15 ℃～25 ℃ in the reaction process, and the time is 3.5～6.5 hours.After reaction finishes, there is a large amount of crystallizations to occur in the reactor bottom, after filtration, be washed to washing lotion and show neutral, dry, the resultant of collecting from reaction mixture is a white crystals, through infrared spectra, nucleus magnetic resonance and ultimate analysis, prove that the crystallization of white is product Trimethylolhexane trinitrate.The yield of resultant Trimethylolhexane trinitrate can reach 94.0%.
Embodiment 5
The nitric-sulfuric acid of 98% concentrated nitric acid and 20% oleum composition is added in the reactor as nitrating agent, under well-stirred condition, add the raw material Trimethylolhexane in the reactor in batches, the mol ratio of Trimethylolhexane and nitric acid is 1: 30, nitric acid and vitriolic mass ratio are 30～40: 70～60, after reinforced the finishing, continue reaction, temperature is controlled at 0 ℃～15 ℃ in the reaction process, and the time is 3～5 hours.After reaction finishes, there is a large amount of crystallizations to occur in the reactor bottom, after filtration, be washed to washing lotion and show neutral, dry, the resultant of collecting from reaction mixture is a white crystals, through infrared spectra, nucleus magnetic resonance and ultimate analysis, prove that the crystallization of white is product Trimethylolhexane trinitrate.The yield of resultant Trimethylolhexane trinitrate can reach 96%.
Claims (5)
1, a kind of Trimethylolhexane trinitrate is characterized in that molecular formula is C
9H
17O
9N
3, chemical structural formula is:
2, a kind of preparation method of Trimethylolhexane trinitrate, it is characterized in that: by Trimethylolhexane as raw material, synthesizing trimethylol hexane trinitrate under the effect of nitrating agent, earlier nitrating agent is added in the reactor, Trimethylolhexane is added in batches again, control reaction temperature is-5～30 ℃, reaction times is 0.5～7 hour, after reaction is finished, collect resultant from reaction mixture, resultant is the Trimethylolhexane trinitrate;
Above-mentioned nitrating agent is the nitric-sulfuric acid of concentrated nitric acid, anhydrous nitric acid, concentrated nitric acid and the vitriol oil or concentrated nitric acid and oleum composition; The mol ratio of Trimethylolhexane and nitric acid is 1: 4～30; The mass ratio of nitric acid, sulfuric acid and water is 5～25: 90～60 in the nitric-sulfuric acid nitrating agent that the concentrated nitric acid and the vitriol oil are formed: 5～15; Nitric acid and vitriolic mass ratio are 30～40: 70～60 in the nitric-sulfuric acid nitrating agent that concentrated nitric acid and oleum are formed.
3, the preparation method of Trimethylolhexane trinitrate according to claim 2 adds urea as catalyzer when it is characterized in that synthesizing trimethylol hexane trinitrate, earlier nitrating agent is added in the reactor during reaction, catalyzer is added again.
4, the preparation method of Trimethylolhexane trinitrate according to claim 3, the add-on that it is characterized in that above-mentioned catalyzer is 1～10% of Trimethylolhexane by mass percentage.
5, the preparation method of Trimethylolhexane trinitrate according to claim 2 is characterized in that above-mentioned esterification reaction temperature is 0～15 ℃, and the nitrated time is 0.5～5 hour, and the mol ratio of Trimethylolhexane and nitric acid is 1: 7～25.
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| CN103980128B (en) * | 2014-05-29 | 2016-01-20 | 西南科技大学 | 2,6-dinitrobenzene is to the synthetic method of two benzylalcohol nitric ethers |
| CN107619370B (en) * | 2017-11-10 | 2020-06-23 | 西安近代化学研究所 | Preparation method of trimethylolethane trinitrate |
| CN109574850B (en) * | 2018-12-29 | 2021-11-12 | 宜宾北方川安化工有限公司 | Industrial reaction method of trimethylolethane trinitrate |
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Effective date of registration: 20060113 Address after: 030051 Department of chemical engineering, North China Institute of technology, Shanxi, Taiyuan Applicant after: Zhongbei Univ Address before: 030051 Department of chemical engineering, North China Institute of technology, Shanxi, Taiyuan Applicant before: Cui Jianlan |
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