CN114213253A - Preparation method for synthesizing p-dinitrosobenzene by wet material - Google Patents

Preparation method for synthesizing p-dinitrosobenzene by wet material Download PDF

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CN114213253A
CN114213253A CN202111580211.3A CN202111580211A CN114213253A CN 114213253 A CN114213253 A CN 114213253A CN 202111580211 A CN202111580211 A CN 202111580211A CN 114213253 A CN114213253 A CN 114213253A
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dinitrosobenzene
wet
benzoquinone dioxime
stirring
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CN114213253B (en
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齐永新
梁玉飞
胡盼
徐慧慧
史哲
肖丁元
朱月
吕德斌
周正勇
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Tianyuan Aviation Materials Yingkou Technology Co ltd
Tianyuan Hangzhou New Material Technology Co ltd
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Tianyuan Hangzhou New Material Technology Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/06—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by nitrosation of hydrocarbons or substituted hydrocarbons
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract

The application discloses a preparation method for synthesizing p-dinitrosobenzene by wet materials, which comprises the following steps: adding phenol into aqueous solution of sodium nitrite and sodium hydroxide to prepare mixed solution of sodium phenolate and sodium nitrite, dropwise adding the mixed solution into sulfuric acid solution at a preset temperature, stirring for reaction, filtering and washing to prepare an intermediate p-nitrosophenol wet material; dropwise adding a hydroxylamine hydrochloride water solution into the intermediate p-nitrosophenol wet material, stirring for reaction, filtering and washing to obtain a p-benzoquinone dioxime wet material; dissolving the p-benzoquinone dioxime wet material in a sodium hydroxide aqueous solution to obtain an alkaline p-benzoquinone dioxime solution, dropwise adding the NaClO dilute solution into the alkaline p-benzoquinone dioxime solution, stirring for reaction, filtering and washing to obtain a p-dinitrosobenzene product. The method has the advantages of low cost of raw materials, simple operation process, no need of drying wet intermediate in the process, and excellent adhesive property of the finally prepared p-dinitrosobenzene, and only water is involved in the whole process as a reaction solvent.

Description

Preparation method for synthesizing p-dinitrosobenzene by wet material
Technical Field
The invention belongs to the field of chemical raw material production, and particularly relates to a preparation method of a chemical raw material p-dinitrosobenzene.
Background
P-dinitrosobenzene (1,4-dinitrosobenzene) is a vulcanizing agent with brown powder or solid appearance, is called 1,4-dinitrosobenzene by a name, has the molecular weight of 136.11, the melting point of 146.5 ℃ and the density of 1.4175, and is mainly used for vulcanizing and bonding colloids such as butyl rubber, natural rubber, styrene-butadiene rubber and the like.
The rubber-metal composite piece integrates the characteristics of rubber and metal, and is widely applied in the industries of automobiles, machinery, national defense and the like, and the key of the use reliability of the rubber-metal composite piece is the firm bonding between the rubber and the metal. With the progress of science and technology and the development of economy, the synthetic adhesive is replacing mechanical connection more and more, the application of the adhesive has been expanded to many fields, an effective way is provided for simplifying the process, saving energy, reducing cost and improving economic benefit of various industries, and the adhesive becomes a fine chemical industry with great development prospect. The rubber-metal bonding is achieved by vulcanization bonding except that the process cannot be operated or the base material is unstable under the hot vulcanization condition. Therefore, the adhesive used for vulcanization bonding has been widely studied, and new adhesives are continuously emerging. Polynitroso aromatic compounds, particularly dinitrosobenzene, are widely used in these adhesives because of their excellent adhesion-promoting effect. The quality of dinitrosobenzene products directly influences the vulcanization adhesion performance, and the high-quality dinitrosobenzene can effectively improve the adhesion effect on rubber.
The dinitrobenzene may be present in polymeric or associated form. Therefore, the chemical reactivity to dinitrosobenzene varies depending on the manner of sample preparation. For example, samples of p-dinitrosobenzene prepared by Ruggli and Petitjean reacted almost quantitatively with aniline, while other samples did not react at all. Similar differences were found in reactivity to dinitrosobenzene vulcanizate-like materials. The effect of highly reactive dinitrosobenzene in the vulcanization of elastomeric synthetic rubbers requires a relatively greater amount of less reactive dinitrosobenzene to do so. Similar differences between the active and inactive samples under the same basic assay conditions cannot be explained by simple analytical judgment, and the actual chemical differences of the products are not clear, but may be differences in reactivity due to differences in structure and degree of polymerization.
The p-dinitrosobenzene was prepared by oxidation in an alkaline solution using potassium ferricyanide in the early stage, but since potassium ferricyanide has a large molecular weight, two parts of potassium ferricyanide are required for oxidation of one part of p-benzoquinone dioxime, and a relatively large amount of potassium ferricyanide is required for this reaction. In addition to the cost, this process has other disadvantages, in particular when the product is used for vulcanizing elastomeric materials, the removal of the large amount of ferrocyanide formed in the reaction is very difficult, since the dinitrobenzene falls in a tightly split state, and therefore the ferrocyanide is blocked, requiring a large amount of water and a considerable time to remove this impurity. Removal of ferrocyanide is an important step because, like other ionic bonding materials, it has a negative impact on the electrical insulation properties of the polymer vulcanizate. Moreover, ferrocyanide is an oxidation catalyst and can significantly reduce the aging resistance of the polymer.
The most practical way of synthesizing p-dinitrosobenzene is currently that set forth in U.S. Pat. No. 2,2419976, which is carried out by oxidizing an alkaline solution of p-benzoquinone dioxime with an alkali metal hypochlorite or hypobromite, at a relatively low temperature, so that no significant amount of dinitroso compound is oxidized to dinitro. The substitution of hypohalite for potassium ferricyanide allows the amount of oxidizing agent used and the electrolyte in the product to be reduced and p-dinitrosobenzene synthesized in this manner, which has high reactivity in the vulcanization of synthetic rubber materials, to be obtained in excellent yields. However, p-benzoquinone dioxime, which is an industrial raw material for synthesizing p-dinitrosobenzene, has high cost, and large dust in dry powder during construction operation, and potential problems such as dust pollution and dust explosion are to be solved.
Disclosure of Invention
The embodiment of the invention aims to provide a method for synthesizing p-dinitrosobenzene by using wet materials, which solves the problems that the quality of rubber materials is reduced, or the synthesis process is complex, the raw material cost is high, the use of the raw materials has potential danger and the like, which are caused by difficulty in removing byproducts in the traditional technology.
According to the embodiment of the application, the preparation method for synthesizing the p-dinitrosobenzene by the wet material comprises the following steps:
(1) adding phenol into aqueous solution of sodium nitrite and inorganic base to prepare mixed solution of sodium phenolate and sodium nitrite, dropwise adding the mixed solution into sulfuric acid solution at a preset temperature, stirring for reaction, filtering and washing to prepare intermediate p-nitrosophenol wet material;
(2) dropwise adding hydroxylamine hydrochloride water solution into the intermediate p-nitrosophenol wet material at a preset temperature, stirring for reaction, filtering and washing to obtain a p-benzoquinone dioxime wet material;
(3) dissolving the p-benzoquinone dioxime wet material in an aqueous solution of inorganic base to obtain an alkaline p-benzoquinone dioxime solution, dropwise adding a NaClO dilute solution with 5-10% of available chlorine into the alkaline p-benzoquinone dioxime solution under the conditions of preset temperature and complete light-proof treatment of a reaction process environment, stirring for reaction, filtering and washing to obtain a p-dinitrosobenzene product.
The structural formula of the method for preparing p-dinitrosobenzene is as follows:
Figure BDA0003426905070000031
preferably, in (1) and (2), the molar ratio of the phenol, the sodium nitrite, the inorganic base, the sulfuric acid and the hydroxylamine hydrochloride is 1.0 (1.0-2.0): 1.0-1.5): 1.0-3.0): 1.0-2.0.
Preferably, in the step (1), the preset temperature is-25-5 ℃, and the dripping time is 1-5 hours.
Preferably, in (1), the washing effect of the washing process is such that the pH value of the filtrate measured is neutral.
Preferably, in (2), the predetermined temperature is 40 to 70 ℃.
Preferably, in the step (3), the mass ratio of benzoquinone dioxime, inorganic base and water in the wet material of benzoquinone dioxime is 1:0.53: 12.5.
Preferably, in (3), the dropping time is from 0.5 to 2 hours.
Preferably, in (3), the molar ratio of benzoquinone dioxime to sodium hypochlorite in the wet p-benzoquinone dioxime feed is 1.0 (0.8-1.5).
Preferably, in the step (3), the preset temperature is 5-25 ℃, and the dripping time is 1-4 hours.
Preferably, in (3), the washing effect of the washing process is such that the pH value of the filtrate measured is neutral.
The method starts from the most basic substrate phenol, three steps of reactions are continuous without interruption, and wet intermediates involved in the synthesis process are directly used for the synthesis of dinitrosobenzene without being dried.
It should be noted that, in the synthesis process, the three-step reaction is continuous without interruption, and the related intermediate wet materials do not need to be dried. In the reaction process, the mixed solution, the hydroxylamine hydrochloride aqueous solution and the NaClO dilute solution are added continuously at a constant speed. In the reaction process, the solid content of the wet material p-benzoquinone dioxime is calculated by testing the water content. During the reaction, the effective chlorine test value of the NaClO solution has a shelf life of 2 days.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
according to the embodiment, the p-dinitrosobenzene product is finally obtained by starting from phenol and performing three-step continuous kettle type reaction on the raw materials, the method is low in raw material cost, only water is involved in the whole process as a reaction solvent, the operation process is simple, the wet material of the intermediate product in the process does not need to be dried, the process is simplified, and the finally prepared p-dinitrosobenzene has excellent adhesive bonding performance. The method is suitable for industrial production or continuous expansion production of dinitrosobenzene products, and has good application prospect. Wherein, the reaction process intermediates p-nitrosophenol and p-benzoquinone dioxime can also be dried and directly used as chemical products for sale (p-benzoquinone dioxime is also one of the widely applied heat vulcanizing agent products in the market at present).
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
FIG. 1 is an infrared spectrum of a dinitrosobenzene sample obtained in examples 1 to 8, in which the ordinate of each example is independent of each other.
Fig. 2 is an enlarged view of a portion of fig. 1, in which the ordinate of the infrared spectrum is under a uniform standard.
FIG. 3 is an infrared spectrum of a dinitrosobenzene sample obtained in example 9 to example 17, wherein the ordinate of each example is independent of each other.
Fig. 4 is a partial enlarged view of fig. 3, wherein the ordinate of the infrared spectrum is under a uniform standard.
FIG. 5 is an infrared spectrum of a dinitrosobenzene sample obtained in example 1 and comparative example 1, in which the ordinate of each example is independent of each other.
Fig. 6 is a partial enlarged view of fig. 5, wherein the ordinate of the infrared spectrum is under a uniform standard.
Detailed Description
The exemplary embodiments will be described herein in detail, and the embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present application.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
Example 1:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,137.99g) and sodium hydroxide (1.5mol,60.12g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.60g), stirring to dissolve the phenol to obtain a mixed solution 1; slowly adding concentrated sulfuric acid (3mol,294.78g) into 535mL of ice water, and stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2mol,139.54g) into 109mL of tap water, and stirring to dissolve to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 132.09). A sample (5.1203g) was placed in a forced air oven and dried to constant weight (3.4429g) and the solids content of the sample was determined: 67.24%, p-benzoquinone dioxime yield: 60.5 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.618mol,126.97g, wet material) in aqueous solution (970mL) of sodium hydroxide (1.12mol,44.96g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (8.62 percent of available chlorine, 0.680mol,559.54g) into 405mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 69.23g, yield: 82.30% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.52 percent.
In the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3And the like.
Example 2:
firstly, adding 483mL of tap water into sodium nitrite (1.0mol,69.21g) and sodium hydroxide (1.5mol,60.23g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.52g), stirring to dissolve the phenol to obtain a mixed solution 1; slowly adding concentrated sulfuric acid (3mol,294.03g) into 535mL of ice water, and stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2mol,139.02g) into 109mL of tap water, and stirring to dissolve to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 112.76). A sample (5.0022g) was placed in a forced air oven and dried to constant weight (3.7071g) and the solids content of the sample was determined: 74.11%, yield of p-benzoquinone dioxime: 60.5 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.578mol,107.76g, wet material) in aqueous solution (970mL) of sodium hydroxide (1.05mol,42.06g) to prepare alkaline p-benzoquinone dioxime solution 4; adding NaClO solution (available chlorine 8.62%, 0.636mol,523.42g) into 379mL tap water to prepare dilute solution 5 of NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 63.86g, yield: 81.17% (calculated on p-benzoquinone dioxime as raw material). Burning residues: 0.28 percent.
In the embodiment, the ratio of the first-step substrate sodium nitrite is 1.5 equivalents, and can also be 1.0 equivalent or any equivalent between 1.0 and 2.0 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 3:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.11g) and sodium hydroxide (1.0mol,40.34g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.42g), and stirring to dissolve the phenol to obtain a mixed solution 1; slowly adding concentrated sulfuric acid (3mol,294.12g) into 535mL of ice water, and stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2mol,139.24g) into 109mL of tap water, and stirring to dissolve to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 120.59 g). A sample (5.0045g) was placed in a forced air oven and dried to constant weight (3.5082g) and the solids content of the sample was determined: 70.10%, p-benzoquinone dioxime yield: 61.20 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.587mol,115.59g, wet material) in aqueous solution (1013mL) of sodium hydroxide (1.07mol,42.67g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (8.54 percent of available chlorine, 0.645mol and 536.05g) into 380mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 63.95g, yield: 80.10% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.24 percent.
In this embodiment, the ratio of the first-step substrate sodium hydroxide is 1.0 equivalent, and may be 1.2 equivalents or any equivalent between 1.0 and 1.5 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 4:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.45g) and sodium hydroxide (1.5mol,60.02g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.15g), stirring to dissolve the phenol to obtain a mixed solution 1; slowly adding concentrated sulfuric acid (1mol,98.17g) into 535mL of ice water, and stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2mol,138.99g) into 109mL of tap water, and stirring to dissolve to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 105.75 g). A sample (5.2051g) was placed in a forced air oven and dried to constant weight (4.0142g) and the solids content of the sample was determined: 77.12%, p-benzoquinone dioxime yield: 59.04 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.561mol,100.54g, wet material) in aqueous solution (946mL) of sodium hydroxide (1.02mol,40.84g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (8.12 percent of available chlorine, 0.617mol,539.50g) into 337mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 62.04g, yield: 78.02% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.62 percent.
In this embodiment, the ratio of the first-step substrate concentrated sulfuric acid is 2.0 equivalents, and may also be 1.0 equivalent or any equivalent between 1.0 and 3.0 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 5:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.12g) and sodium hydroxide (1.5mol,60.14g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.13g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,295.31g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (1.0mol,169.57g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 123.37 g). A sample (4.8920g) was placed in a forced air oven and dried to constant weight (3.3838g) and the solids content of the sample was determined: 69.17%, p-benzoquinone dioxime yield: 61.78 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.593mol,118.48g, wet material) in aqueous solution (987.88mL) of sodium hydroxide (1.08mol,43.16g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (7.87% of available chlorine, 0.653mol,588.33g) into 338mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 66.04g, yield: 81.78% (calculated by using p-benzoquinone dioxime as a raw material), ignition residue: 0.64 percent.
The ratio of the substrate hydroxylamine hydrochloride in the second step in this embodiment is 1.5 equivalents, and may be 1.0 equivalent or any equivalent between 1.0 and 2.0 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 6:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.15g) and sodium hydroxide (1.5mol,60.21g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.42g), stirring to dissolve the phenol and obtaining a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.14g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the ambient temperature of-12 ℃, maintaining the system temperature at-10 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,138.99g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 118.04 g). A sample (5.3020g) was placed in a forced air oven and dried to constant weight (3.9341g) and the solids content of the sample was determined: 74.20%, p-benzoquinone dioxime yield: 63.41 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.606mol,112.74g, wet material) in aqueous solution (1017mL) of sodium hydroxide (1.10mol,44.06g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (7.61% of available chlorine, 0.666mol,621.06g) into 324mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 67.60g, yield: 82.01% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.50 percent.
In the embodiment, the reaction temperature of the first step is-10 ℃, or can be-25 ℃ or any temperature between-25 ℃ and 5 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third reactions in this example may be usedIs KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 7:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.10g) and sodium hydroxide (1.5mol,60.27g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.07g), and stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.45g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the ambient temperature of-27 ℃, maintaining the system temperature at-25 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.07g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 121.21 g). A sample (5.0301g) was placed in a forced air oven and dried to constant weight (3.4778g) and the solids content of the sample was determined: 69.14%, p-benzoquinone dioxime yield: 60.67 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.582mol,116.18g, wet material) in aqueous solution (968mL) of sodium hydroxide (1.06mol,42.30g) to prepare alkaline p-benzoquinone dioxime solution 4; adding 284mL of tap water into a NaClO solution (7.28% of available chlorine, 0.666mol,623.38g) to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 63.17g, yield: 79.81% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.45 percent.
In the embodiment, the reaction temperature of the first step is-25 ℃, or can be-25 ℃ or any temperature between-25 ℃ and 5 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 8:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.08g) and sodium hydroxide (1.5mol,60.19g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.15g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.19g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (1 hour) dropwise adding the solution 1 into the solution 2 at the ambient temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.17g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 127.12 g). A sample (5.1012g) was placed in a forced air oven and dried to constant weight (3.4678g) and the solids content of the sample was determined: 67.98%, p-benzoquinone dioxime yield: 62.56 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.600mol,122.02g, wet material) in an aqueous solution (998mL) of sodium hydroxide (1.09mol,43.70g) to prepare an alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (7.28% of available chlorine, 0.661mol,643.72g) into 294mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 65.99g, yield: 80.74% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.74 percent.
In the embodiment, the dripping time of the first step reaction is 1 hour, and can also be 5 hours or any time between 1 and 5 hours;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 9:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.30g) and sodium hydroxide (1.5mol,60.08g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.35g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.09g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (5 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.16g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 130.67 g). A sample (5.2143g) was placed in a forced air oven and dried to constant weight (3.4279g) and the solids content of the sample was determined: 65.74%, p-benzoquinone dioxime yield: 62.19 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.597mol,125.46g, wet material) in aqueous solution (988mL) of sodium hydroxide (1.09mol,43.44g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (7.10 percent of available chlorine, 0.657mol,656.29g) into 276mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 66.16g, yield: 81.41% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.64 percent.
In the embodiment, the dripping time of the first step reaction is 5 hours, and can also be 5 hours or any time between 1 and 5 hours;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 10:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,137.98g) and sodium hydroxide (1.5mol,60.30g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.35g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.31g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.00g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at an ambient temperature of 56 ℃, maintaining the system temperature at 55 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 128.70 g). A sample (5.1452g) was placed in a forced air oven and dried to constant weight (3.5198g) and the solids content of the sample was determined: 68.41%, p-benzoquinone dioxime yield: 63.74 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.612mol,123.56g, wet material) in aqueous solution (1017mL) of sodium hydroxide (1.11mol,44.52g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (7.10% of available chlorine, 0.673mol,672.59g) into 283mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 68.50g, yield: 82.24% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.78 percent.
In the embodiment, the second step reaction temperature is 55 ℃, or 70 ℃ or any temperature between 40 ℃ and 70 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 11:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.14g) and sodium hydroxide (1.5mol,60.17g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.41g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.1g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the ambient temperature of 5 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.04g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at an ambient temperature of 71 ℃, maintaining the system temperature at 70 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 110.73 g). A sample (5.0241g) was placed in a forced air oven and dried to constant weight (3.8746g) and the solids content of the sample was determined: 77.12%, p-benzoquinone dioxime yield: 61.82%;
thirdly, dissolving wet p-benzoquinone dioxime (0.5mol,105.70g, wet material) in aqueous solution (1018.97mL) of sodium hydroxide (1.11mol,42.93g) to prepare alkaline p-benzoquinone dioxime solution 4; adding NaClO solution (available chlorine 6.87%, 0.673mol,670.38g) into 250.72mL of tap water to prepare dilute solution 5 of NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 64.16g, yield: 79.87% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.71 percent.
In the embodiment, the reaction temperature of the second step is 70 ℃, and can be any temperature between 40 ℃ and 70 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 12:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,137.99g) and sodium hydroxide (1.5mol,60.07g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.15g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.31g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.12g) into 109mL tap water, stirring and dissolving to obtain a solution 3; at an ambient temperature of 42 ℃, the solution 3(0.5 hour) is dropwise added into an aqueous solution of an intermediate p-nitrosophenol wet material, the system temperature is maintained at 40 ℃, stirring is continued for 2 hours after the addition is finished, and the p-benzoquinone dioxime wet material (wet weight: 117.44g) is prepared by filtration and washing. A sample (5.2310g) was placed in a forced air oven and dried to constant weight (3.8767g) and the solids content of the sample was determined: 74.11%, yield of p-benzoquinone dioxime: 63.01 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.602mol,112.21g, wet material) in aqueous solution (1010mL) of sodium hydroxide (1.09mol,43.80g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (6.87% of available chlorine, 0.662mol and 683.89g) into 256mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 65.34g, yield: 79.74% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.62%, ignition residue: 0.80 percent.
In the embodiment, the dripping time of the second step reaction is 0.5 hour, and can be any time between 0.5 and 2 hours;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 13:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.13g) and sodium hydroxide (1.5mol,60.14g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.15g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.12g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,138.97g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 124.03 g). A sample (5.6871g) was placed in a forced air oven and dried to constant weight (4.0606g) and the solids content of the sample was determined: 71.40%, p-benzoquinone dioxime yield: 64.11 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.612mol,118.34g, wet material) in aqueous solution (1022mL) of sodium hydroxide (1.11mol,44.50g) to prepare alkaline p-benzoquinone dioxime solution 4; adding NaClO solution (available chlorine 6.51%, 0.918mol,533.31g) into 161mL tap water to prepare dilute solution 5 of NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 60.15g, yield: 72.25% (calculated by using p-benzoquinone dioxime as a raw material), ignition residue: 0.62 percent.
In this embodiment, the ratio of the substrate sodium hypochlorite in the third step is 1.5 equivalents, or 0.8 equivalents or any equivalent between 0.8 and 1.5 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 14:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.11g) and sodium hydroxide (1.5mol,60.10g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.31g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.31g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.21g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 123.15 g). A sample (5.1413g) was placed in a forced air oven and dried to constant weight (3.6041g) and the solids content of the sample was determined: 70.10%, p-benzoquinone dioxime yield: 62.50 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.599mol,118.01g, wet material) in aqueous solution (999mL) of sodium hydroxide (1.11mol,43.57g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (available chlorine 6.74%, 0.479mol,945.62g) into 329mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 62.46g, yield: 76.62% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.54 percent.
In the third step of the present embodiment, the ratio of the substrate sodium hypochlorite is 0.8 equivalent, or any equivalent between 0.8 and 1.5 equivalents;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 15:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.05g) and sodium hydroxide (1.5mol,60.07g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.09g), and stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.21g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.28g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 144.13 g). A sample (5.0403g) was placed in a forced air oven and dried to constant weight (3.0161g) and the solids content of the sample was determined: 59.84%, yield of p-benzoquinone dioxime: 62.44 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.603mol,139.09g, wet material) in aqueous solution (985mL) of sodium hydroxide (1.10mol,43.84g) to prepare alkaline p-benzoquinone dioxime solution 4; adding NaClO solution (available chlorine 6.21%, 0.663mol,757.23g) into 183mL tap water to prepare dilute solution 5 of NaClO solution with 5% available chlorine; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 26 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 25 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 64.83g, yield: 79.05% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.67 percent.
In the embodiment, the reaction temperature of the second step is 25 ℃, and can be 5 ℃ or any temperature between 5 ℃ and 25 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 16:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.01g) and sodium hydroxide (1.5mol,60.03g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.09g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.41g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.13g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 119.44 g). A sample (5.4102g) was placed in a forced air oven and dried to constant weight (3.9505g) and the solids content of the sample was determined: 73.02%, p-benzoquinone dioxime yield: 63.14 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.603mol,114.03g, wet material) in aqueous solution (1010mL) of sodium hydroxide (1.10mol,43.85g) to prepare alkaline p-benzoquinone dioxime solution 4; adding NaClO solution (available chlorine 6.51%, 0.663mol,940.85g) into 218.23mL tap water to prepare dilute solution 5 of NaClO solution with the available chlorine of 5%; dropwise adding the solution 5(4 hours) into the solution 4 at the environmental temperature of 4 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 5 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 61.13g, yield: 74.50% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.36 percent.
In the embodiment, the reaction temperature of the second step is 5 ℃, and can be any temperature between 5 ℃ and 25 ℃;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Example 17:
firstly, adding 483mL of tap water into sodium nitrite (2.0mol,138.12g) and sodium hydroxide (1.5mol,60.13g), stirring to completely dissolve the sodium nitrite and the sodium hydroxide, adding phenol (1.0mol,94.27g), stirring to dissolve the phenol to obtain a mixed solution 1; adding concentrated sulfuric acid (3.0mol,294.14g) slowly into 535mL of ice water, stirring and diluting to obtain a solution 2;
slowly (2 hours) dropwise adding the solution 1 into the solution 2 at the environmental temperature of 3 ℃, maintaining the system temperature at 5 ℃, continuously stirring for 2 hours after the addition is finished, filtering and washing to obtain an intermediate p-nitrosophenol wet material;
secondly, adding hydroxylamine hydrochloride (2.0mol,139.01g) into 109mL tap water, stirring and dissolving to obtain a solution 3; dropwise adding the solution 3(2 hours) into an aqueous solution of an intermediate p-nitrosophenol wet material at the ambient temperature of 42 ℃, maintaining the system temperature at 40 ℃, continuously stirring for 2 hours after the addition, filtering and washing to obtain a p-benzoquinone dioxime wet material (wet weight: 125.88 g). A sample (5.0014g) was taken and placed in a forced air oven and dried to constant weight (3.4690g) and the solids content of the sample was determined: 69.36%, p-benzoquinone dioxime yield: 63.21 percent;
thirdly, dissolving wet p-benzoquinone dioxime (0.607mol,120.88g, wet material) in aqueous solution (1011mL) of sodium hydroxide (1.10mol,44.16g) to prepare alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (6.01 percent of available chlorine, 0.668mol,788.18g) into 159mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(1 hour) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after adding, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 66.43g, yield: 80.41% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.76 percent.
In the embodiment, the dripping time of the third step reaction is 1 hour, and can be any time between 1 and 4 hours;
in the embodiment, before the third step of reaction synthesis, the effective chlorine of the NaClO solution is measured, and the effective chlorine value is effective within two days;
NaOH in the first and third step reaction in this example may be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
Comparative example 1:
p-benzoquinone dioxime (1.086mol,150.14g, dry matter) was dissolved in an aqueous solution (1875mL) of sodium hydroxide (1.97mol,78.91g) to prepare an alkaline p-benzoquinone dioxime solution 4; adding a NaClO solution (6.57 percent of available chlorine, 1.195mol,1694.96g) into 405mL of tap water to prepare a dilute solution 5 of the NaClO solution with the available chlorine of 5 percent; dropwise adding the solution 5(4 hours) into the solution 4 at the ambient temperature of 13 ℃ under the condition that the reaction container is completely protected from light, maintaining the system temperature at 15 ℃, continuously stirring at the natural temperature for 2 hours after the addition is finished, filtering, pulping, washing and drying to obtain a p-dinitrosobenzene product, wherein the dry weight is as follows: 118.91g, yield: 80.45% (calculated by taking p-benzoquinone dioxime as a raw material), ignition residue: 0.69 percent.
In the comparative example, intermediate p-benzoquinone dioxime was used as a purchased powder product;
in the comparative example, the effective chlorine of the NaClO solution is measured before reaction synthesis, and the effective chlorine value is effective within two days;
NaOH in the reaction of the comparative example can also be KOH or NaHCO3、Na2CO3、KHCO3、K2CO3Any one of the above alternatives.
The yields, appearance properties and physical and chemical index data of dinitrosobenzene samples obtained in examples 1 to 17 and comparative example 1 are shown in Table 1; the data of evaluation of the application properties of dinitrosobenzene samples obtained in examples 1 to 17 and comparative example 1 are shown in Table 2; example 1-example 8 the infrared spectrum data obtained for dinitrosobenzene samples are shown in fig. 1 and fig. 2; the data of the infrared spectrum of the dinitrosobenzene sample obtained in example 9-example 17 are shown in FIG. 3 and FIG. 4; the data of the infrared spectra of the dinitrosobenzene samples obtained in example 1 and comparative example 1 are shown in fig. 5 and fig. 6.
TABLE 1 data and test of physicochemical indices for dinitrosobenzene samples from example 1 to example 17 and comparative example 1
Figure BDA0003426905070000251
As can be seen from table 1, in examples 1 to 12, in the case where the reaction conditions of the third step were not changed, example 4 reduced the stoichiometric equivalent of sulfuric acid, which resulted in a decrease in the yield of dinitrosobenzene as the final product; other conditions are changed, and the final product has little influence on the yield and appearance of dinitrosobenzene. Compared with the example 1, the reduction of the proportioning equivalent of the phenol and other substrates can reduce the yield of the intermediate p-benzoquinone dioxime, especially the reduction of equivalent of sodium nitrite and sulfuric acid; the reduction of the temperature and the change of the dropping speed in the first nitrosation process, and the increase of the condensation temperature and the increase of the dropping speed in the second condensation process have little influence on the yield of the intermediate p-benzoquinone dioxime, but the yields are not as good as those of example 1.
Compared with the comparative example 1, in the example with the same reaction conditions in the third step, except that the yield and the appearance of the sample in the example 4 are different, the yield, the appearance and the burning residue of the product obtained by feeding the wet benzoquinone dioxime and the dry material are not obviously different in other examples.
In the examples 13 to 17, the ratio of sodium hypochlorite and the reaction temperature affect the change of the yield and the appearance of the product without changing the reaction conditions of the first two steps, and especially, the color of the product is obviously darker due to the increase of the ratio and the increase of the temperature.
The ignition residues of all the product samples of the examples or the comparative examples are less than or equal to 0.8 percent, and the data are relatively observable.
TABLE 2 application Performance evaluation data for example 1-example 17 and comparative example 1 on dinitrosobenzene samples
Figure BDA0003426905070000261
Note: 1. preparing samples of all examples and the sample of the comparative example 1 to evaluate the bonding performance;
r is the proportion of rubber attached to the bonding surface after bonding and stripping, and the ideal damage form is 100R.
As can be seen from Table 2, all the examples and comparative samples exhibited excellent adhesion test performance; in the examples of examples 1 to 12, the adhesion property data of the dinitrosobenzene samples measured in the examples were not significantly different from the data of the sample of comparative example 1 without changing the reaction conditions of the third step and the same property evaluation test conditions; in examples 13 to 17, the bonding performance data of the dinitrosobenzene samples and the performance data of the ethylene propylene diene monomer rubber adhesives of examples 13 and 15 were relatively poor when the reaction conditions of the third step were changed.
As can be seen from fig. 1, fig. 2, fig. 3 and fig. 4, in the examples of example 1 to example 12, the infrared spectrogram data peak patterns and the special absorption peak regions (symmetric and antisymmetric stretching vibration absorption peaks of a nitro functional group N ═ O) of the samples of the examples are observed without changing the reaction conditions of the third step, and the change of the reaction conditions of the first two steps has little influence on the infrared data of the final product dinitrosobenzene; in examples 13 to 17, the reaction conditions of the third step were changed, the ir spectrum of the dinitrosobenzene by the sample changed very obviously, and excessive sodium hypochlorite equivalent, temperature increase or anti-dropping time all resulted in excessive oxidation of the final product, which resulted in the prominent special absorption peak area of nitro group in the ir spectrum data and poor ir spectrum overlapping.
From fig. 5 and 6, it can be seen that the infrared spectra of the samples obtained in comparative example 1 and example 1 almost completely overlap under the same reaction conditions.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It will be understood that the present application is not limited to the precise arrangements that have been described above and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.

Claims (10)

1. A preparation method for synthesizing p-dinitrosobenzene by wet materials is characterized by comprising the following steps:
(1) adding phenol into aqueous solution of sodium nitrite and inorganic base to prepare mixed solution of sodium phenolate and sodium nitrite, dropwise adding the mixed solution into sulfuric acid solution at a preset temperature, stirring for reaction, filtering and washing to prepare intermediate p-nitrosophenol wet material;
(2) dropwise adding hydroxylamine hydrochloride water solution into the intermediate p-nitrosophenol wet material at a preset temperature, stirring for reaction, filtering and washing to obtain a p-benzoquinone dioxime wet material;
(3) dissolving the p-benzoquinone dioxime wet material in an aqueous solution of inorganic base to obtain an alkaline p-benzoquinone dioxime solution, dropwise adding a NaClO dilute solution with 5-10% of available chlorine into the alkaline p-benzoquinone dioxime solution under the conditions of preset temperature and complete light-proof treatment of a reaction process environment, stirring for reaction, filtering and washing to obtain a p-dinitrosobenzene product.
2. A process for preparing p-dinitrosobenzene in wet mass as claimed in claim 1, wherein the molar ratio of phenol, sodium nitrite, inorganic base, sulfuric acid and hydroxylamine hydrochloride in (1) and (2) is 1.0 (1.0-2.0) (1.0-1.5) (1.0-3.0) to (1.0-2.0).
3. The process for producing p-dinitrosobenzene as claimed in claim 1, wherein the predetermined temperature in (1) is-25 to 5 ℃ and the dropping time is 1 to 5 hours.
4. A process for preparing p-dinitrosobenzene as wet material according to claim 1, wherein in (1), the washing effect of the washing process is neutral as measured by pH of the filtrate.
5. The process for preparing p-dinitrosobenzene in wet mass according to claim 1, wherein the predetermined temperature in (2) is 40 to 70 ℃.
6. The process according to claim 1, wherein the wet p-dinitrosobenzene comprises benzoquinone dioxime, inorganic base and water in the wet p-benzoquinone dioxime feed in the ratio of 1:0.53:12.5 by mass.
7. A process for preparing p-dinitrosobenzene as a wet material according to claim 1, wherein in (3), the dropping time is 0.5-2 hours.
8. A process for preparing p-dinitrosobenzene in wet form as claimed in claim 1, wherein in (3), the molar ratio of benzoquinone dioxime to sodium hypochlorite in the wet material of p-benzoquinone dioxime is 1.0 (0.8-1.5).
9. The process for preparing p-dinitrosobenzene in wet mass according to claim 1, wherein in (3), the predetermined temperature is 5 to 25 ℃ and the dropping time is 1 to 4 hours.
10. A process for preparing p-dinitrosobenzene as a wet material according to claim 1, wherein in (3), the washing effect of the washing process is neutral as measured by pH of the filtrate.
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