CN109180536A - A kind of preparation method of nitro-guanyl hydrazine - Google Patents
A kind of preparation method of nitro-guanyl hydrazine Download PDFInfo
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- CN109180536A CN109180536A CN201811173450.5A CN201811173450A CN109180536A CN 109180536 A CN109180536 A CN 109180536A CN 201811173450 A CN201811173450 A CN 201811173450A CN 109180536 A CN109180536 A CN 109180536A
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- hydrazine
- nitro
- guanyl
- nitroguanidine
- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/16—Compounds containing any of the groups, e.g. aminoguanidine
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of nitro-guanyl hydrazine, nitro-guanyl hydrazine is made using guanidine nitrate, the concentrated sulfuric acid, hydration hydrazine reaction, the reaction step includes: that nitroguanidine is made in guanidine nitrate ice solution after the concentrated sulfuric acid is dehydrated, nitroguanidine again with reacted under hydrazine hydrate low temperature be made nitro-guanyl hydrazine, obtain product nitro-guanyl hydrazine using filtering, washing, drying.The present invention has the advantages that the present invention is added using low-temp reaction, substep, the nitro-guanyl hydrazine purity is high of hydrazine hydrate synthesis, impurity content is few, molar yield is high, achieves good economic benefit；Preparation method is safe and environment-friendly, is suitable for industrial production, is with a wide range of applications.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of preparation method of nitro-guanyl hydrazine.
Background technique
Nitro-guanyl hydrazine is the energetic material with Research Prospects, synthesizes corresponding energetic ion salt pair with it for cation
It finds the energetic material haveing excellent performance to have great importance, it was studied as explosive in detail by Univ Munich Germany in recent years
Possibility, detonation property is suitable with cyclotrimethylene trinitramine, but than cyclotrimethylene trinitramine insensitiveness, and at low cost
It is honest and clean.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of nitro-guanyl hydrazine, i.e., fed intake using substep and
Low-temp reaction, the method for making nitroguanidine be converted into nitro-guanyl hydrazine safe and efficiently.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of preparation method of nitro-guanyl hydrazine, innovation
Point is: the preparation method is dehydrated through the concentrated sulfuric acid using guanidine nitrate and nitroguanidine is made, and nitroguanidine and hydrazine hydrate are to add in batches
Mode low-temp reaction be made nitro-guanyl hydrazine；Specifically comprise the following steps:
S1, a certain amount of concentrated sulfuric acid is added in round-bottomed flask, is then turned on stirring, guanidine nitrate is slowly added into the concentrated sulfuric acid,
And temperature≤30 DEG C are controlled, charging rate is controlled in 30-40min；
After S2, guanidine nitrate feed intake, it is warming up to 38-42 DEG C, keeps the temperature 30-40min, the material dissolved；
S3, the material of dissolution is added to progress ice solution in a certain amount of ice water, after ice solution temperature reaches 25 DEG C, filtering, washing
Obtain nitroguanidine；
S4, nitroguanidine is put into the hydrazine hydrate of part, is kept stirring and at the uniform velocity stirs；Then remaining hydrazine hydrate is added dropwise, and controls temperature
60 DEG C of < of degree；
It is warming up to 58-62 DEG C after S5, hydrazine hydrate completion of dropwise addition, keeps the temperature 8-10h, after reaction, is cooled to 15-20 DEG C, filter,
Washing obtains nitro-guanyl hydrazine.
Reaction principle:
Further, the concentrated sulfuric acid uses mass percentage concentration than the concentrated sulfuric acid for 98% in the S1.
Further, the mass ratio of guanidine nitrate, the concentrated sulfuric acid and water ice solution is 1:2.1:8 in the S1 and S3.
Further, the molar ratio of nitroguanidine and hydrazine hydrate is 1:1.02 in the S4.
The present invention has the advantages that the preparation method of nitro-guanyl hydrazine of the present invention, is generated using nitroguanidine and hydrazine hydrate
During nitro-guanyl hydrazine, since there are side reactions in the reaction, the present invention is using the control of the method for low temperature and Multistep feeding
The generation of side reaction, so that the content of nitro-guanyl hydrazine reaches 98.0%, reaction yield reaches >=90.0%, and then through the invention
The nitro-guanyl hydrazine product purity of preparation is high, impurity content is few, molar yield is high, achieves good economic benefit, and this hair
Bright preparation method is safe and environment-friendly, is suitable for industrial production.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment
Present embodiment discloses a kind of preparation method of nitro-guanyl hydrazine, the preparation method is fed intake using substep and low temperature
The mode of reaction, specific step is as follows for the preparation method:
Embodiment 1
The 210g concentrated sulfuric acid is added in 500ml round-bottomed flask, is slowly added to 100g guanidine nitrate, charging rate control after opening stirring
In 30min, feed temperature is no more than 30 DEG C, after guanidine nitrate adds, and is to slowly warm up to 40 DEG C, will after insulation reaction 0.5h
Material is added in 800g ice water, and filtering, washing obtain nitroguanidine after quickly stirring is cooled to 25 DEG C.
20g hydrazine hydrate is added in 500ml round-bottomed flask, opens stirring and is slowly added to 130g nitroguanidine, stirred to nitroguanidine
After mixing uniformly, residue 31g hydrazine hydrate is added dropwise, control temperature is not higher than 60 DEG C, and after being added dropwise, 60 DEG C of heat preservation 8h, reaction terminates
After filter, divide equally 2 cleaning products with 100g clear water, obtain nitro-guanyl hydrazine 98.2g.Nitro-guanyl hydrazine is through liquid in the present embodiment
It is 98.1% that analysis of hplc, which obtains content, and nitro-guanyl hydrazine molar yield is 90.0%.
Embodiment 2
The 210g concentrated sulfuric acid is added in 500ml round-bottomed flask, is slowly added to 100g guanidine nitrate, charging rate control after opening stirring
In 35min, feed temperature is no more than 30 DEG C, after guanidine nitrate adds, and is to slowly warm up to 42 DEG C, will after insulation reaction 0.5h
Material is added in 800g ice water, and filtering, washing obtain nitroguanidine after quickly stirring is cooled to 25 DEG C.
20g hydrazine hydrate is added in 500ml round-bottomed flask, opens stirring and is slowly added to 130g nitroguanidine, stirred to nitroguanidine
After mixing uniformly, residue 31g hydrazine hydrate is added dropwise, control temperature is not higher than 60 DEG C, and after being added dropwise, 62 DEG C of heat preservation 8h, reaction terminates
After filter, divide equally 2 cleaning products with 100g clear water, obtain nitro-guanyl hydrazine 98.5g.Nitro-guanyl hydrazine is through liquid in the present embodiment
It is 98.0% that analysis of hplc, which obtains content, and nitro-guanyl hydrazine molar yield is 90.2%.
Embodiment 3
The 210g concentrated sulfuric acid is added in 500ml round-bottomed flask, is slowly added to 100g guanidine nitrate, charging rate control after opening stirring
In 40min, feed temperature is no more than 30 DEG C, after guanidine nitrate adds, and is to slowly warm up to 38 DEG C, will after insulation reaction 0.5h
Material is added in 800g ice water, and filtering, washing obtain nitroguanidine after quickly stirring is cooled to 25 DEG C.
20g hydrazine hydrate is added in 500ml round-bottomed flask, opens stirring and is slowly added to 130g nitroguanidine, stirred to nitroguanidine
After mixing uniformly, residue 31g hydrazine hydrate is added dropwise, control temperature is not higher than 60 DEG C, and after being added dropwise, 58 DEG C of heat preservation 8h, reaction terminates
After filter, divide equally 2 cleaning products with 100g clear water, obtain nitro-guanyl hydrazine 98.5g.Nitro-guanyl hydrazine is through liquid in the present embodiment
It is 98.3% that analysis of hplc, which obtains content, and nitro-guanyl hydrazine molar yield is 90.5%.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (4)
1. a kind of preparation method of nitro-guanyl hydrazine, it is characterised in that: the preparation method is dehydrated using guanidine nitrate through the concentrated sulfuric acid
Nitroguanidine is made, nitro-guanyl hydrazine is made in nitroguanidine and the hydrazine hydrate low-temp reaction in a manner of to add in batches；It specifically includes as follows
Step:
S1, a certain amount of concentrated sulfuric acid is added in round-bottomed flask, is then turned on stirring, guanidine nitrate is slowly added into the concentrated sulfuric acid,
And temperature≤30 DEG C are controlled, charging rate is controlled in 30-40min；
After S2, guanidine nitrate feed intake, it is warming up to 38-42 DEG C, keeps the temperature 30-40min, the material dissolved；
S3, the material of dissolution is added to progress ice solution in a certain amount of ice water, after ice solution temperature reaches 25 DEG C, filtering, washing
Obtain nitroguanidine；
S4, nitroguanidine is put into the hydrazine hydrate of part, is kept stirring and at the uniform velocity stirs；Then remaining hydrazine hydrate is added dropwise, and controls temperature
60 DEG C of < of degree；
It is warming up to 58-62 DEG C after S5, hydrazine hydrate completion of dropwise addition, keeps the temperature 8-10h, after reaction, is cooled to 15-20 DEG C, filter,
Washing obtains nitro-guanyl hydrazine.
2. the preparation method of nitro-guanyl hydrazine according to claim 1, it is characterised in that: the concentrated sulfuric acid uses matter in the S1
Percentage concentration is measured than the concentrated sulfuric acid for 98%.
3. the preparation method of nitro-guanyl hydrazine according to claim 1, it is characterised in that: guanidine nitrate in the S1 and S3,
The mass ratio of the concentrated sulfuric acid and water ice solution is 1:2.1:8.
4. the preparation method of nitro-guanyl hydrazine according to claim 1, it is characterised in that: nitroguanidine and hydration in the S4
The molar ratio of hydrazine is 1:1.02.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811173450.5A CN109180536A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of nitro-guanyl hydrazine |
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| CN201811173450.5A CN109180536A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of nitro-guanyl hydrazine |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077371A (en) * | 1997-02-10 | 2000-06-20 | Automotive Systems Laboratory, Inc. | Gas generants comprising transition metal nitrite complexes |
| CN101497579A (en) * | 2009-03-26 | 2009-08-05 | 里程 | Green process for producing nitroguanidine |
| WO2013003977A1 (en) * | 2011-07-01 | 2013-01-10 | 合肥星宇化学有限责任公司 | Compound of 2,5-disubstituted-3-nitroimino-1,2,4-triazoline and preparation method and use as pesticide thereof |
| CN104557619A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds |
-
2018
- 2018-10-09 CN CN201811173450.5A patent/CN109180536A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077371A (en) * | 1997-02-10 | 2000-06-20 | Automotive Systems Laboratory, Inc. | Gas generants comprising transition metal nitrite complexes |
| CN101497579A (en) * | 2009-03-26 | 2009-08-05 | 里程 | Green process for producing nitroguanidine |
| WO2013003977A1 (en) * | 2011-07-01 | 2013-01-10 | 合肥星宇化学有限责任公司 | Compound of 2,5-disubstituted-3-nitroimino-1,2,4-triazoline and preparation method and use as pesticide thereof |
| CN104557619A (en) * | 2014-12-30 | 2015-04-29 | 中国农业大学 | Methoxyimino phenylacetate compounds containing nitrohydrazinecarboximidamide structures as well as preparation method and application of methoxyimino phenylacetate compounds |
Non-Patent Citations (3)
| Title |
|---|
| A.A.ASTRAT"YEV ET AL: "Synthesis and Some Properties of 1,2-Dinitroguanidine", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| SIJIA XUE ET AL: "Synthesis and Insecticidal Activities of 1,5-Disubstituted-1,3,5-hexahydrotriazine-2-N-nitroimines", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
| 杨冬燕等: "芳亚甲基硝基缩氨基胍类化合物的合成及杀虫活性", 《高等学校化学学报》 * |
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Application publication date: 20190111 |