A toluenesulfonyldiazodiphenylphosphine compound and its preparation method and application

Abstract

The present invention belongs to the technical field of organic synthesis, and discloses a toluenesulfonyldiazodiphenylphosphine compound, a preparation method and application thereof. The structural formula of the toluenesulfonyldiazodiphenylphosphine compound is shown in Formula I. The preparation method comprises the following preparation steps: adding p-toluenesulfonylhydrazine to an organic solvent, stirring and dissolving evenly, cooling to 5-10°C, then dripping diphenylphosphine chloride and stirring at room temperature for reaction; after the reaction is completed, heating to 40-50°C, then dripping hydrogen peroxide, heating to reflux temperature for reflux reaction, standing and stratifying after the reaction is completed to remove the aqueous phase layer, taking the organic phase for concentration and crystallization, and obtaining a toluenesulfonyldiazodiphenylphosphine compound. The toluenesulfonyldiazodiphenylphosphine compound of the present invention can be used as a photoinitiator. The synthesis method is simple, the reaction conditions are mild, the raw material sources are wide, the production cost is low, and it is easy to be industrialized and applied.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a toluenesulfonyldiazodiphenylphosphine compound and a preparation method and application thereof. Background Art

[0002] Diphenylphosphine compounds are widely used in flame retardants and light stabilizers, and in dyes, pigments, and medicine. Tosyl has strong electrophilicity and good stability, which makes it widely used in organic synthesis. First, tosyl can react with nucleophiles as an electrophilic reagent to generate new compounds. For example, tosyl can react with amines to generate sulfonamide compounds, or with alcohols to generate sulfonate compounds. These reactions are widely used in drug synthesis and natural product synthesis. At the same time, sulfonates are also widely used in flame retardants, dispersants, and other fields. However, there are few reports on new structural compounds obtained by combining diphenylphosphine compounds with tosyl and their use as photoinitiators. Summary of the invention

[0003] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a toluenesulfonyldiazodiphenylphosphine compound (SPN).

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned tosyldiazodiphenylphosphine compound.

[0005] Another object of the present invention is to provide the use of the above-mentioned tosyldiazodiphenylphosphine compound as an ultraviolet light initiator.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A toluenesulfonyldiazodiphenylphosphine compound, the structural formula of which is shown in the following formula I:

[0008]

[0009] The preparation method of the above-mentioned tosyldiazodiphenylphosphine compound comprises the following preparation steps:

[0010] (1) adding p-toluenesulfonyl hydrazide to an organic solvent, stirring and dissolving it uniformly, cooling it to 5-10° C., then adding diphenylphosphine chloride dropwise, and stirring and reacting at room temperature after the addition is complete;

[0011] (2) After the reaction in step (1) is completed, the temperature is raised to 40-50° C., hydrogen peroxide is added dropwise, and the temperature is raised to reflux temperature for reflux reaction. After the reaction is completed, the aqueous phase is removed by standing and the organic phase is concentrated and crystallized to obtain a tosyldiazodiphenylphosphine compound.

[0012] Furthermore, the organic solvent in step (1) is ethylene dichloride.

[0013] Furthermore, in the process of dropwise adding diphenylphosphine chloride in step (1), the temperature of the reaction system is controlled to be below 25°C.

[0014] Furthermore, the stirring reaction time in step (1) is 3 to 5 hours.

[0015] Furthermore, in step (1), the molar ratio of p-toluenesulfonyl hydrazide to diphenylphosphonium chloride is 0.9 to 1.1:1.

[0016] Furthermore, in step (2), the molar ratio of the hydrogen peroxide added to p-toluenesulfonyl hydrazide is 2 to 3:1 based on the hydrogen peroxide content.

[0017] Furthermore, the reflux reaction time in step (2) is 2 to 3 hours.

[0018] Furthermore, the crystallization temperature in step (2) is 5 to -5°C.

[0019] The synthetic route of the above reaction is as follows:

[0020]

[0021] The above-mentioned tosyldiazodiphenylphosphine compound is used as a UV initiator. It can be applied to UV curing of white ink systems for plastics and PCBs. It has the advantages of strong adhesion, light resistance, yellowing resistance, high temperature resistance, high hardness, etc.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The toluenesulfonyldiazodiphenylphosphine compound provided by the present invention contains both a diphenylphosphine compound structure and a benzenesulfonyl structure, and further introduces a diazo linking group, which can combine or improve the application performance of the two and broaden its application range.

[0024] (2) The synthesis method of the present invention is simple, the reaction conditions are mild, the raw materials are widely available, the purity and yield of the obtained product are high, the production cost is low, and it is easy to apply industrially.

[0025] (3) The toluenesulfonyldiazodiphenylphosphine compound provided by the present invention has obvious ultraviolet absorption and initiation characteristics, and can be applied to the ultraviolet curing of white ink systems for plastics and PCBs, and has the advantages of strong adhesion, light resistance, yellowing resistance, high temperature resistance, high hardness, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the infrared spectrum of the tosyldiazodiphenylphosphine compound obtained in the example;

[0027] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the tosyldiazodiphenylphosphine compound obtained in the example;

[0028] Figure 3 This is a diagram showing the appearance of the tosyldiazodiphenylphosphine compound obtained in the example;

[0029] Figure 4 The figure is the UV scanning spectrum of the tosyldiazodiphenylphosphine compound obtained in the example. DETAILED DESCRIPTION

[0030] The present invention is further described in detail below in conjunction with embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0031] Example 1

[0032] A method for preparing a toluenesulfonyldiazodiphenylphosphine compound comprises the following preparation steps:

[0033] (1) Add p-toluenesulfonyl hydrazide (186 g) and 500 ml of dichloroethane to a 3-liter flask, mix and stir to dissolve evenly, and cool the temperature to 5°C. Add diphenylphosphonium chloride (220 g) dropwise to the flask, and control the temperature below 25°C. After the addition is complete, keep the mixture at room temperature for 4 hours.

[0034] (2) After the reaction in step (1) is completed, the temperature is raised to 40-50°C, and hydrogen peroxide (250 g, 30 wt%) is added dropwise to the flask. After the addition is complete, the temperature is slowly raised to reflux and refluxed for 2.5 hours. After the reaction is completed, water is separated and 300 ml of the product dichloroethane is evaporated. The temperature is lowered to about 0°C, and a large amount of white crystalline solid is produced, which is the product tosyldiazodiphenylphosphine compound (SPN).

[0035] The toluenesulfonyldiazodiphenylphosphine compound obtained in this example was tested to have a purity of 96.1% and a yield of 96.4%.

[0036] The infrared spectrum and hydrogen nuclear magnetic resonance spectrum of the tosyldiazodiphenylphosphine compound obtained in this example are as follows: Figure 1 and Figure 2 The above identification spectrum proves that the target product is obtained.

[0037] The tosyldiazodiphenylphosphine compound obtained in this example is in the form of white crystals, and its appearance is shown in the figure below. Figure 3 shown.

[0038] The UV scanning spectrum of the tosyldiazodiphenylphosphine compound obtained in this example is as follows: Figure 4 As shown. Figure 4It can be seen that the tosyldiazodiphenylphosphine compound obtained by the present invention has obvious ultraviolet absorption and excitation characteristics.

[0039] Application of the toluenesulfonyldiazodiphenylphosphine compound obtained in this example in UV curing of protective adhesive ink for plastics such as PVC gussets, floor tiles, PET, PC, etc.:

[0040] The ink composition is: prepolymer (aliphatic acrylic polyurethane) 46.25%; UV monomer (TMPTA, ethoxylated trimethylolpropane triacrylate) 30%; titanium dioxide 20%; initiator SPN 3%; leveling agent (polydimethylsiloxane) 0.5%, defoaming agent (polyether silicone oil) 0.2%, and inhibitor HQ 0.05%.

[0041] The obtained ink can be completely cured by irradiating with UV lamp for 15 seconds. The obtained protective glue has the advantages of strong adhesion, light resistance, yellowing resistance, high temperature resistance, high hardness, etc.

[0042] Example 2

[0043] A method for preparing a toluenesulfonyldiazodiphenylphosphine compound comprises the following preparation steps:

[0044] (1) Add p-toluenesulfonyl hydrazide (170 g) and 500 ml of dichloroethane to a 3-liter flask, mix and stir to dissolve evenly, and cool to 10°C. Add diphenylphosphonium chloride (220 g) dropwise to the flask, and control the temperature below 25°C. After the addition is complete, keep the mixture at room temperature for 3 hours.

[0045] (2) After the reaction in step (1) is completed, the temperature is raised to 40-50°C, and hydrogen peroxide (250 g, 30 wt%) is added dropwise to the flask. After the addition is complete, the temperature is slowly raised to reflux and refluxed for 2 hours. After the reaction is completed, water is separated and 350 ml of the product dichloroethane is evaporated. The temperature is lowered to about 0°C, and a large amount of white crystalline solid is produced, which is the product tosyldiazodiphenylphosphine compound (SPN).

[0046] The toluenesulfonyldiazodiphenylphosphine compound obtained in this example was tested to have a purity of 95.7% and a yield of 96.3%.

[0047] Example 3

[0048] A method for preparing a toluenesulfonyldiazodiphenylphosphine compound comprises the following preparation steps:

[0049] (1) Add p-toluenesulfonyl hydrazide (200 g) and 500 ml of dichloroethane to a 3-liter flask, mix and stir until evenly dissolved, and cool to 10°C. Add diphenylphosphonium chloride (220 g) dropwise to the flask, and control the temperature below 25°C. After the addition is complete, keep the mixture at room temperature for 5 hours.

[0050] (2) After the reaction in step (1) is completed, the temperature is raised to 40-50° C., and hydrogen peroxide (250 g, 30 wt%) is added dropwise to the flask. After the addition is completed, the temperature is slowly raised to reflux and refluxed for 3 hours. After the reaction is completed, water is separated and 350 ml of the product dichloroethane is evaporated. The temperature is lowered to about 0° C., and a large amount of white crystalline solid is produced, which is the product tosyldiazodiphenylphosphine compound (SPN).

[0051] The toluenesulfonyldiazodiphenylphosphine compound obtained in this example was tested to have a purity of 95.6% and a yield of 96.2%.

[0052] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A use of a toluenesulfonyldiazodiphenylphosphine compound as an ultraviolet light initiator, characterized in that: The structural formula of the tosyldiazodiphenylphosphine compound is shown in the following formula I: Formula Ⅰ.

2. The use of a tosyldiazodiphenylphosphine compound as a UV initiator according to claim 1, characterized in that: The tosyldiazodiphenylphosphine compound is prepared by the following method: (1) Add p-toluenesulfonyl hydrazide to an organic solvent and stir to dissolve evenly, cool to 5-10°C, then drop diphenylphosphine chloride, and stir at room temperature to react after the dropwise addition is complete; (2) After the reaction in step (1) is completed, the temperature is raised to 40-50°C, and hydrogen peroxide is added dropwise, and the temperature is raised to reflux temperature for reflux reaction. After the reaction is completed, the aqueous phase is removed by standing and the organic phase is concentrated and crystallized to obtain a tosyldiazodiphenylphosphine compound.

3. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: The organic solvent in step (1) is ethylene dichloride.

4. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: In the process of adding diphenylphosphine chloride in step (1), the temperature of the reaction system is controlled to be below 25°C.

5. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: The stirring reaction time in step (1) is 3 to 5 hours.

6. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: The molar ratio of p-toluenesulfonyl hydrazide to diphenylphosphine chloride added in step (1) is 0.9-1.1:

1.

7. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: The molar ratio of the hydrogen peroxide added in step (2) to p-toluenesulfonyl hydrazide is 2-3:1 based on the hydrogen peroxide content.

8. The use of a toluenesulfonyldiazodiphenylphosphine compound as a UV initiator according to claim 2, characterized in that: The reflux reaction time in step (2) is 2 to 3 hours.

9. The use of a toluenesulfonyldiazodiphenylphosphine compound as an ultraviolet light initiator according to claim 2, characterized in that: The crystallization temperature in step (2) is 5~-5°C.

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