阅读说明：本技术 二氰胺过渡金属盐及其制备方法 (Dicyandiamide transition metal salt and preparation method thereof ) 是由 李志敏 张同来 张建国 王林 钟野 于 2019-09-02 设计创作，主要内容包括：本发明涉及二氰胺过渡金属盐及其制备方法。该类化合物的结构通式如下图所示,式中M表示金属离子：Cr、Mn、Fe、Co、Ni、Cu、Zn等；n表示金属离子的价态数或者是二氰胺根离子的数量：1、2、3、4等。将过渡金属硝酸盐、盐酸盐或乙酸盐与二氰胺钠反应得到二氰胺过渡金属盐。该类金属盐对高氯酸铵等固体推进剂氧化剂燃烧分解具有良好的催化效果,有作为固体推进剂燃烧催化剂的应用价值。本发明不含重金属元素,环境友好,并且制备方法简单、条件温和、原材料成本低廉。<Image he="159" wi="398" file="DDA0002187782120000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to dicyandiamide transition metal salts and a preparation method thereof. The structural general formula of the compound is shown as the following figure, wherein M represents metal ions: cr, Mn, Fe, Co, Ni, Cu, Zn, etc.; n represents the valence number of the metal ion or the number of dicyanamide ions: 1. 2, 3, 4, etc. The transition metal nitrate, hydrochloride or acetate reacts with sodium dicyanamide to obtain dicyanamide transition metal salt. The metal salt has good catalytic effect on the combustion decomposition of solid propellant oxidants such as ammonium perchlorate and the like, and has application value as a solid propellant combustion catalyst. The invention does not contain heavy metal elements, is environment-friendly, and has simple preparation method, mild condition and low cost of raw materials.)

1. Dicyandiamide transition metal salts, characterized in that: the series of compounds consists of transition metal ions and dicyanamide ions, and the structural general formula is as follows, wherein n represents the valence number of the metal ions or the number of the dicyanamide ions: 1. 2, 3, 4, etc.

2. The transition metal atom according to claim 1, wherein: and M is selected from any one of Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd.

3. the process for producing dicyandiamide transition metal salt according to claim 1, characterized in that: dropwise adding the transition metal salt solution into the dicyandiamide sodium solution, or dropwise adding the dicyandiamide sodium solution into the transition metal salt solution, reacting for a period of time at a certain temperature, cooling to room temperature, filtering out a precipitate product, washing with cold water and ethanol, and drying to obtain the dicyandiamide transition metal salt.

4. The process for producing dicyandiamide transition metal salt according to claim 3, characterized in that: the transition metal salt is any one of nitrate, hydrochloride or acetate of the metal described in claim 2.

5. The process for producing dicyandiamide transition metal salt according to claim 3, characterized in that: the solvent of the solution is one or more of water, methanol, ethanol, hexanenitrile, acetone and N, N-dimethylformamide.

6. The process for producing dicyandiamide transition metal salt according to claim 3, characterized in that: the concentration of the transition metal salt solution is 0.01-1M, and the concentration of the dicyandiamide sodium solution is 0.01-1M.

7. The process for producing dicyandiamide transition metal salt according to claim 3, characterized in that: the reaction time is 0.1-8 h.

8. the process for producing dicyandiamide transition metal salt according to claim 3, characterized in that: the reaction temperature is 10-90 ℃.

Technical Field

The invention relates to the technical field of combustion catalysis of solid rocket propellants, in particular to dicyandiamide transition metal salt and a preparation method thereof.

Background

The solid propellant is an energetic material which can stably combust to release a large amount of high-temperature gas, is a power energy source of weapons such as strategic missiles, tactical missiles, space vehicles, kinetic energy interception missiles and the like, has good and bad performance, directly influences the survival capability and the operational efficiency of the weapons, and has great significance for the development of the national defense industry. The combustion performance is the core of the solid propellant technology, and plays a role in determining the shooting precision and range of rocket weapons and the working reliability of engines. The addition of a certain amount of combustion catalyst in the propellant formula is an effective way to further improve the combustion performance of the solid propellant, and is receiving wide attention.

Solid propellant combustion catalysts are mostly substances containing metallic elements: metal powder, metal oxide, metal hydroxide, organic and inorganic metal salt, metal complex and the like, and composite catalysts of the metal powder, the metal oxide, the metal hydroxide, the organic and inorganic metal salt, the metal complex and the like with other materials (such as carbon nano tubes and graphene). Compounds such as ferric oxide, ferrocene and its derivatives, lead citrate, lead salicylate, etc. have good combustion catalytic performance.

The organic cation salt of dicyanamide radical can generate spontaneous combustion reaction when contacting with a strong oxidant, and has potential as a spontaneous combustion liquid propellant fuel, wherein the dicyanamide radical plays a key role in the reaction. Dicyandiamide transition metal salt is easy to react with a strong oxidant, and the introduction of metal elements causes the dicyandiamide transition metal salt to show a good combustion catalysis effect.

Disclosure of Invention

The invention aims to provide dicyandiamide transition metal salt and a preparation method thereof, the compound has catalytic action on thermal decomposition and combustion of solid propellant components, and the preparation method is simple, mild in condition and low in cost.

In order to achieve the above objects, the present invention provides dicyandiamide transition metal salts having the following general structural formula:

Wherein n represents the valence number of the metal ion or the number of dicyanamide ions: 1. 2, 3, 4, etc.

Further, the transition metal atom M is any one of Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd.

The invention also provides a preparation method of the dicyandiamide transition metal salt, which comprises the following steps:

Dropwise adding the transition metal salt solution into the dicyandiamide sodium solution, or dropwise adding the dicyandiamide sodium solution into the transition metal salt solution, reacting for a period of time at a certain temperature, cooling to room temperature, filtering out a precipitate product, washing with cold water and ethanol, and drying to obtain the dicyandiamide transition metal salt.

according to the scheme, a transition metal salt solution can be used as a reaction base solution, and a dicyandiamide sodium solution is dropwise added into the reaction base solution; it is also possible to use a solution of sodium dicyandiamide as a base solution to which a solution of a transition metal salt is added dropwise.

According to the scheme, the transition metal salt is any one of nitrate, hydrochloride or acetate of Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd.

According to the scheme, the solvent of the transition metal salt solution is one or more of water, methanol, ethanol, hexanenitrile, acetone and N, N-dimethylformamide.

According to the scheme, the solvent of the dicyandiamide sodium solution is one or more of water, methanol, ethanol, hexanenitrile, acetone and N, N-dimethylformamide.

According to the scheme, the concentration of the transition metal salt solution is 0.01-1M.

According to the scheme, the concentration of the dicyandiamide sodium solution is 0.01-1M.

According to the scheme, the molar ratio of the transition metal salt to the dicyandiamide sodium is 2: 1-1: 8.

According to the scheme, the reaction time is 0.1-8 h.

According to the scheme, the reaction temperature is 10-90 ℃.

The invention has the following beneficial effects:

The invention relates to dicyandiamide transition metal salt and a preparation method thereof, and the dicyandiamide transition metal salt has the advantages that:

(1) The dicyandiamide in the dicyandiamide transition metal salt has high reaction activity under the action of dicyandiamide radicals and an oxidant, the transition metal ions have good catalytic action on combustion, and the three-dimensional framework structure is favorable for dispersing the catalytic ions. Is a potential solid rocket propellant combustion catalyst.

(2) the dicyandiamide transition metal salt of the present invention has low sensitivity and high safety.

(3) The dicyandiamide transition metal salt does not contain heavy metal elements such as Pd, Bi and the like, and is green and environment-friendly.

(4) The dicyandiamide transition metal salt preparation method has the advantages of easily available raw materials, simple process, mild conditions and contribution to realizing industrial production.

Drawings

FIG. 1 is a diagram of the skeletal structure of copper dicyandiamide (viewed along the b-axis);

FIG. 2 is a diagram of the skeletal structure of cobalt dicyandiamide (viewed along the a-axis);

FIG. 3 is a DSC curve of ammonium perchlorate with catalyst.

Detailed Description

The invention is further illustrated, but not limited, by the following specific examples.