阅读说明：本技术 一种环保检测试剂偶氮氯膦mN的制备方法 (Preparation method of environmental protection detection reagent azochlorophosphine mN ) 是由 杨金瑞 刘文渊 李斌 李玉龙 司晓汉 徐博刚 于 2019-11-20 设计创作，主要内容包括：本发明公开一种环保检测试剂偶氮氯膦mN的制备方法,步骤如下：⑴提纯原料偶氮氯膦I；⑵制备偶氮氯膦mN；⑶次日用盐酸酸化至pH为1后,放置5-8小时即有沉淀析出,过滤出反应液中的固体,并将过滤出的固体浸泡到浓盐酸中,浸泡1小时以上,再次过滤出固体,能够再根据实际需要重复上述浸泡步骤,最后在80-100℃的真空干燥箱中干燥,即得环保检测试剂偶氮氯膦mN。本发明方法步骤简单,操作容易,易于实现产业化生产且生产加工时间短,极大地提高了生产效率,缩短了工时；同时,该方法在生产时不必再采用加价格昂贵的专用设备,并能降低生产成本,提高了企业的市场竞争能力,使偶氮氯膦mN能够在市场上得到更大的推广应用。(The invention discloses a preparation method of an environment-friendly detection reagent, namely, azochlorophosphine mN, which comprises the following steps of ⑴ purifying a raw material, ⑵ preparing the azochlorophosphine mN, ⑶ times of daily hydrochloric acid is acidified to pH of 1, then the raw material is placed for 5-8 hours to precipitate, solid in a reaction solution is filtered, the filtered solid is soaked in concentrated hydrochloric acid for more than 1 hour, the solid is filtered again, the soaking step can be repeated according to actual needs, and finally the solid is dried in a vacuum drying box at 80-100 ℃ to obtain the environment-friendly detection reagent, namely, the azochlorophosphine mN.)

1. A preparation method of an environmental protection detection reagent azochlorophosphine mN is characterized by comprising the following steps: the method comprises the following steps:

⑴ purification of raw material azo-chlorophosphine I

Dissolving solid powder of raw material azochlorophosphine I in ten times of warm pure water of the raw material azochlorophosphine I at 60-80 ℃, then filtering the solution while the solution is hot, further removing insoluble substances, then adding concentrated hydrochloric acid into the filtered solution, standing overnight, precipitating solids the next day, filtering out solids in reaction liquid, and soaking the filtered solids into the concentrated hydrochloric acid to obtain solid: the weight ratio of concentrated hydrochloric acid is 1: 1-1.1, soaking for more than 1 hour, filtering out solids again, repeating the soaking step according to actual needs, and finally drying in a vacuum drying oven at 80-100 ℃, thus completing the purification of the paraazochlorophosphine I;

⑵ preparation of azochlorophosphine mN

Putting m-nitroaniline and hydrochloric acid serving as raw materials into a reactor with a refrigerating device, an electric stirrer, a thermometer and a titration feeder, then opening the electric stirrer to uniformly dissolve the m-nitroaniline serving as the raw material into the hydrochloric acid, simultaneously opening the refrigerating device to cool the reaction kettle to below 0 ℃, dropwise adding a sodium nitrite solution with the mass concentration of 25% which is prepared in advance, generating heat along with the temperature rise of a system when the sodium nitrite solution is dropwise added, continuously stirring for 1 hour after the dropwise adding is finished by controlling the dropwise adding speed and adjusting the refrigerating device and continuously stirring to ensure that the temperature of the reaction system is not higher than 5 ℃, and filtering to remove insoluble substances to obtain a diazonium salt intermediate solution;

wherein, m-nitroaniline: hydrochloric acid: ratio g of sodium nitrite solution: g: l is 1: 1-1.1: 1.6;

cleaning a reactor with a refrigeration device, an electric stirrer, a thermometer and a titration feeder, and then adding purified azochlorophosphine I and a lithium hydroxide solution as raw materials, wherein the mass ratio of the azochlorophosphine I: the mass ratio of the lithium hydroxide solution is 1.5-2: 1, starting electric stirring to uniformly dissolve the raw material azo chlorophosphine I into a lithium hydroxide solution, simultaneously starting a refrigerating device to cool the reaction kettle to below 0 ℃, adding the prepared diazonium salt intermediate solution under strong stirring, dropwise adding the prepared diazonium salt intermediate solution into the reaction kettle, generating heat in reaction along with the temperature rise of a system when the diazonium salt intermediate solution is dropwise added, controlling the dropwise adding speed and adjusting the refrigerating device by continuously stirring to ensure that the reaction system does not exceed 2 ℃, adjusting the pH value to 9-10 after the addition is finished, continuously stirring for 2 hours, and standing overnight;

the m-nitroaniline: the weight ratio of the azochlorophosphine I is 1: 3-4;

⑶ purification of azo-chlorophosphine mN

Acidifying hydrochloric acid for the next day until the pH value is 1, standing for 5-8 hours to precipitate, filtering out solids in the reaction solution, and soaking the filtered solids in concentrated hydrochloric acid to obtain solids: the weight ratio of concentrated hydrochloric acid is 1: 1-1.1, soaking for more than 1 hour, filtering out solids again, repeating the soaking step according to actual needs, and finally drying in a vacuum drying oven at 80-100 ℃ to obtain the environmental protection detection reagent, namely the azochlorophosphine mN.

2. The method for preparing azochlorophosphine mN as the environment-friendly detection reagent according to claim 1, which is characterized in that: the raw materials used in the method are all reagent grade.

Technical Field

The invention belongs to the technical field of organic compound preparation, and particularly relates to a preparation method of an environment-friendly detection reagent azo chlorophosphine mN.

Background

Azochlorophosphine mN has been widely used as an important inorganic ion color developer. The chemical name of the substance is: 2- (4-chloro-2-phosphonophenylazo) -7- (3-nitrophenylazo) -1, 8-dihydroxy-3, 6-naphthalenedisulfonic acid, abbreviated to CPA-mN.

The physicochemical properties are as follows:

dark purplish red crystalline powder. Dissolving in water to give purple red color; insoluble in common organic solvents such as chloroform, diethyl ether and benzene. The inorganic strong acid is green. The strong base appears blue. The red-purple color in acid medium can generate water-soluble green complex with rare earth ions.

Under the current industrial requirements of environmental protection, the analysis of calcium is very important in the processes of environmental detection, environmental monitoring and environmental management, especially in the processes of water quality detection and management. As a novel high-sensitivity display agent, the azochlorophosphine mN has the characteristics of high speed, high efficiency, accuracy, simplicity, convenience and the like. And measuring trace cerium in the titanium and the titanium alloy by using a photometer. Can be used for measuring trace cerium masked in wastewater, iron, nickel and aluminum alloy. And (3) measuring the total amount of the rare earth in samples such as steel and the like by using a luminosity. Trace rare earth elements in rock can also be measured photometrically. However, no method for preparing azochlorophosphine mN which is suitable for industrial mass production and has low cost exists at present.

Through searching, no patent publication related to the present patent application has been found.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a preparation method of an environment-friendly detection reagent azochlorophosphine mN, which is suitable for industrial large-scale production, and has low cost and high production efficiency.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of an environment-friendly detection reagent azochlorophosphine mN comprises the following steps:

⑴ dissolving azochlorophosphine I solid powder in purified water of the azochlorophosphine I at ten times of warm temperature of 60-80 ℃, filtering the solution while hot to remove insoluble substances, adding concentrated hydrochloric acid into the filtered solution, standing overnight, separating out solids the next day, filtering out solids in the reaction solution, soaking the filtered solids in concentrated hydrochloric acid at a weight ratio of 1: 1-1.1 for more than 1 hour, filtering out solids again, repeating the soaking step according to actual needs, and finally drying in a vacuum drying oven at 80-100 ℃ to complete the purification of the paraazo chlorophosphine I;

⑵ preparation of azochlorophosphine mN

Putting m-nitroaniline and hydrochloric acid serving as raw materials into a reactor with a refrigerating device, an electric stirrer, a thermometer and a titration feeder, then opening the electric stirrer to uniformly dissolve the m-nitroaniline serving as the raw material into the hydrochloric acid, simultaneously opening the refrigerating device to cool the reaction kettle to below 0 ℃, dropwise adding a sodium nitrite solution with the mass concentration of 25% which is prepared in advance, generating heat along with the temperature rise of a system when the sodium nitrite solution is dropwise added, continuously stirring for 1 hour after the dropwise adding is finished by controlling the dropwise adding speed and adjusting the refrigerating device and continuously stirring to ensure that the temperature of the reaction system is not higher than 5 ℃, and filtering to remove insoluble substances to obtain a diazonium salt intermediate solution;

wherein, m-nitroaniline: hydrochloric acid: ratio g of sodium nitrite solution: g: l is 1: 1-1.1: 1.6;

cleaning a reactor with a refrigeration device, an electric stirrer, a thermometer and a titration feeder, and then adding purified azochlorophosphine I and a lithium hydroxide solution as raw materials, wherein the mass ratio of the azochlorophosphine I: the mass ratio of the lithium hydroxide solution is 1.5-2: 1, starting electric stirring to uniformly dissolve the raw material azo chlorophosphine I into a lithium hydroxide solution, simultaneously starting a refrigerating device to cool the reaction kettle to below 0 ℃, adding the prepared diazonium salt intermediate solution under strong stirring, dropwise adding the prepared diazonium salt intermediate solution into the reaction kettle, generating heat in reaction along with the temperature rise of a system when the diazonium salt intermediate solution is dropwise added, controlling the dropwise adding speed and adjusting the refrigerating device by continuously stirring to ensure that the reaction system does not exceed 2 ℃, adjusting the pH value to 9-10 after the addition is finished, continuously stirring for 2 hours, and standing overnight;

the m-nitroaniline: the weight ratio of the azochlorophosphine I is 1: 3-4;

⑶ purification of azo-chlorophosphine mN

Acidifying hydrochloric acid for the next day until the pH value is 1, standing for 5-8 hours to precipitate, filtering out solids in the reaction solution, and soaking the filtered solids in concentrated hydrochloric acid to obtain solids: the weight ratio of concentrated hydrochloric acid is 1: 1-1.1, soaking for more than 1 hour, filtering out solids again, repeating the soaking step according to actual needs, and finally drying in a vacuum drying oven at 80-100 ℃ to obtain the environmental protection detection reagent, namely the azochlorophosphine mN.

Moreover, the raw materials used in the method are all reagent grade.

The invention has the advantages and positive effects that:

1. the method has simple steps, easy operation, easy realization of industrialized production and short production and processing time, greatly improves the production efficiency and shortens the working hours; meanwhile, the method does not need to adopt expensive special equipment during production, can reduce the production cost, improves the market competitiveness of enterprises, and enables the azochlorophosphine mN to be popularized and applied in the market.

2. The method carries out purification operation on the raw material azo chlorophosphine I, and has the following specific reasons:

the azo chlorophosphine mN as the product prepared by the invention is an inorganic ion color-developing agent, and the important raw material azo chlorophosphine I for preparing the azo chlorophosphine mN is also an inorganic ion color-developing agent. Although the product price of azochlorophosphine I is far lower than that of azochlorophosphine mN, the unit price is high. Therefore, the azo-chlorophosphine I is either purchased as a raw material or produced and prepared by itself. There is no particular requirement for purification of the starting material. In particular, the raw materials purchased from outsourcing are qualified products. However, according to the results of experiments repeated over the years, the raw material, namely, the azo-chlorophosphine I, prepared by adding the azo-chlorophosphine mN must be purified before the addition reaction.

The specific reasons are as follows: as a product, the inorganic ion color developer does not require chemical purity of a substance as in a general chemical reagent, and is measured accurately. But rather, the product is often judged to be acceptable by sensitivity to a given inorganic ion. That is, a commercially acceptable inorganic ion color developer is only acceptable in terms of its sensitivity to color development of a specific inorganic ion, and its chemical content is not necessarily high in proportion. This creates a hidden danger for the continued reaction. Although purification results in a loss of a certain proportion of the expensive starting material, if the starting material is not purified, the final product will exhibit varying degrees of tarry material in subsequent preparation reactions, with greater losses in the separation process.

Detailed Description

The following detailed description of the embodiments of the present invention is provided for the purpose of illustration and not limitation, and should not be construed as limiting the scope of the invention.

The raw materials used in the invention are conventional commercial products unless otherwise specified; the methods used in the present invention are conventional in the art unless otherwise specified.