Toluenesulfonyl diphenylphosphine compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a toluenesulfonyl diphenylphosphine compound as well as a preparation method and application thereof. The structural formula of the toluenesulfonyl diphenylphosphine compound is as shown in formula I in the specification. The preparation method comprises the following steps: dropwise adding diphenyl phosphorus chloride into water, stirring to react until hydrolysis is complete, and extracting and separating a product to obtain diphenyl phosphorus oxide; and adding the obtained diphenylphosphine oxide into an alkaline aqueous solution for reaction, adding an organic solvent for reflux dehydration after the reaction is completed, dropwise adding 4-toluenesulfonyl chloride and the organic solvent for stirring reaction after the dehydration is completed, adding water for layering after the reaction is completed, and drying an organic phase to remove the solvent, thereby obtaining the toluenesulfonyl diphenylphosphine compound. The toluenesulfonyl diphenylphosphine compound disclosed by the invention can be used as a photoinitiator to be applied to ultraviolet curing of printing ink for plastics and PCBs (Printed Circuit Boards). And the synthesis method is simple, mild in reaction condition, wide in raw material source, relatively low in production cost and easy for industrial application. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a toluenesulfonyl diphenyl phosphine 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 object of the present invention is to provide a toluenesulfonyl diphenyl phosphorus compound (SP).

[0004] Another object of the present invention is to provide a method for preparing the tosyl diphenyl phosphine compound.

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

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

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

[0008]

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

[0010] (1) adding diphenylphosphine chloride dropwise into water, stirring the reaction until hydrolysis is complete, and separating the product by extraction to obtain diphenylphosphine oxide;

[0011] (2) adding the diphenylphosphine obtained in step (1) to an alkaline aqueous solution for reaction, adding an organic solvent for reflux dehydration after the reaction is completed, and then adding 4-toluenesulfonyl chloride and an organic solvent for stirring and reaction after the dehydration is completed. After the reaction is completed, adding water and layering, taking the organic phase, drying and removing the solvent, and obtaining a toluenesulfonyl diphenylphosphine compound.

[0012] Furthermore, the temperature of the dropping process in step (1) is controlled to be below 40°C.

[0013] Furthermore, the stirring reaction in step (1) is carried out at room temperature, and the stirring reaction time is 2 to 4 hours.

[0014] Furthermore, the extraction and separation step in step (1) is as follows: adding dichloroethane to the reaction system for multiple extractions and separations, taking the organic phase, drying and concentrating it, and obtaining a diphenylphosphine mother liquor.

[0015] Furthermore, the molar ratio of the diphenylphosphine chloride in step (1) to the 4-toluenesulfonyl chloride in step (2) is 0.9 to 1.1:1.

[0016] Furthermore, the alkaline aqueous solution in step (2) is a NaOH solution or a KOH solution with a mass concentration of 20% to 30%.

[0017] Furthermore, the organic solvent in step (2) is toluene.

[0018] Furthermore, the stirring reaction temperature in step (2) is 30-40° C., and the stirring reaction time is 3-6 h.

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

[0020]

[0021] The application of the tosyl diphenyl phosphine compound as a UV initiator can be applied to UV curing of acrylic resin ink for plastics and PCBs.

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

[0023] (1) The toluenesulfonyl diphenyl phosphine compound provided by the present invention contains both a diphenyl phosphine compound structure and a benzenesulfonyl structure, which can combine the advantages of both 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 tosyl diphenyl phosphine compound provided by the present invention has been verified to have obvious ultraviolet absorption and initiation characteristics, and can be applied to ultraviolet light curing of acrylic resin inks for plastics and PCBs, and has the advantages of good compatibility and high curing efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the infrared spectrum of the tosyl diphenyl phosphine compound obtained in the example;

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

[0028] Figure 3 This is a morphological diagram of the appearance of the tosyl diphenyl phosphine compound obtained in the example;

[0029] Figure 4 The figure is the UV scanning spectrum of the tosyl diphenyl phosphine 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 tosyl diphenyl phosphine compound comprises the following steps:

[0033] (1) Add 500 g of water to a 3-liter flask, slowly drop 398 g of diphenylphosphine chloride at room temperature, control the dropping temperature to be below 40°C, stir at room temperature for 3 hours after the dropping is completed, and perform tracking detection until the reaction is complete. Add 1000 ml of dichloroethane to extract and separate the liquids several times, dry and filter over anhydrous sodium sulfate, and concentrate the dichloroethane to obtain a diphenylphosphine oxide mother liquor.

[0034] (2) The diphenylphosphine mother liquor obtained in step (1) is added dropwise to a 24% by mass NaOH solution for reaction. After the reaction is completed, toluene is added for reflux dehydration. After the dehydration is completed, a solution of 380 g of 4-toluenesulfonyl chloride and 600 ml of toluene is added dropwise for stirring and reaction. The reaction temperature is controlled to be around 30° C. After the addition is completed, the temperature is kept at 30-40° C. for 4 hours. After the reaction is completed, water is added and the layers are separated. The toluene layer is washed three times with deionized water, and then concentrated and dried to remove the solvent to obtain a toluenesulfonyl diphenylphosphine compound (SP).

[0035] The tosyl diphenyl phosphine compound obtained in this example has a purity of 98.3% and a yield of 90.2%.

[0036] The infrared spectrum and hydrogen nuclear magnetic resonance spectrum of the tosyl diphenyl phosphine 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 tosyl diphenyl phosphine compound obtained in this example is in the form of off-white powder, and its appearance is shown in the figure below. Figure 3 shown.

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

[0039] 1. Application of the tosyl diphenyl phosphine compound obtained in this example in UV curing of LPISM (liquid developing solder resist ink) for PCB:

[0040] The composition of LPISM is: prepolymer (hydroxy acrylate resin ethylene glycol solution) 71.8%; UV monomer (DPHA, dipentaerythritol hexaacrylate) 16%; barium sulfate 5%; initiator SP 4.5%, fumed silica 1%; pigment 1%; leveling agent BYK-405 0.5%; defoamer 0.2%.

[0041] The obtained LPISM can be completely cured by irradiating with UV light for 10 seconds.

[0042] 2. Application of the tosyl diphenyl phosphine compound obtained in this example in UV curing of acrylic resin ink for plastics:

[0043] The ink components are: prepolymer (epoxy acrylate resin) 49.7%; UV monomer (HDDA, hexanediol diacrylate) 25%; pigment 20%; initiator SP 5%; dispersant 0.3%.

[0044] The obtained ink can be completely cured by irradiating with UV lamp for 6 seconds.

[0045] From the above results, it can be seen that the SP photoinitiator obtained in the present invention has a higher UV curing efficiency.

[0046] Example 2

[0047] A method for preparing a tosyl diphenyl phosphine compound comprises the following steps:

[0048] (1) Add 500 g of water to a 3-liter flask, slowly drop 440 g of diphenylphosphine chloride at room temperature, control the dropping temperature to be below 40°C, stir at room temperature for 3 hours after the dropping is completed, and perform tracking detection until the reaction is complete. Add 1000 ml of dichloroethane to extract and separate the liquids several times, dry and filter over anhydrous sodium sulfate, and concentrate the dichloroethane to obtain a diphenylphosphine oxide mother liquor.

[0049] (2) The diphenylphosphine mother liquor obtained in step (1) is added dropwise to a 20% by mass KOH solution for reaction. After the reaction is completed, toluene is added for reflux dehydration. After the dehydration is completed, a solution of 380 g of 4-toluenesulfonyl chloride and 600 ml of toluene is added dropwise for stirring and reaction. The reaction temperature is controlled to be around 30° C. After the addition is completed, the temperature is kept at 30-40° C. for reaction for 5 h. After the reaction is completed, water is added and the layers are separated. The toluene layer is washed twice with deionized water, and then concentrated and dried to remove the solvent to obtain a toluenesulfonyl diphenylphosphine compound.

[0050] The tosyl diphenyl phosphine compound obtained in this example has a purity of 98.7% and a yield of 91.4%.

[0051] Example 3

[0052] A method for preparing a tosyl diphenyl phosphine compound comprises the following steps:

[0053] (1) Add 500 g of water to a 3-liter flask, slowly drop 475 g of diphenylphosphine chloride at room temperature, control the dropping temperature to be below 40°C, stir at room temperature for 4 hours after the dropping is completed, and perform tracking detection until the reaction is complete. Add 1000 ml of dichloroethane to extract and separate the liquids several times, dry and filter over anhydrous sodium sulfate, and concentrate the dichloroethane to obtain a diphenylphosphine oxide mother liquor.

[0054] (2) The diphenylphosphine mother liquor obtained in step (1) is added dropwise to a 30% by mass NaOH solution for reaction. After the reaction is completed, toluene is added for reflux dehydration. After the dehydration is completed, a solution of 380 g of 4-toluenesulfonyl chloride and 600 ml of toluene is added dropwise for stirring and reaction. The reaction temperature is controlled at about 30° C. After the addition is completed, the temperature is kept at 30-40° C. for reaction for 5 h. After the reaction is completed, water is added and the layers are separated. The toluene layer is washed three times with deionized water, and then concentrated and dried to remove the solvent to obtain a toluenesulfonyl diphenylphosphine compound.

[0055] The tosyl diphenyl phosphine compound obtained in this example has a purity of 98.5% and a yield of 90.6%.

[0056] 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 tosyl diphenyl phosphine compound, characterized in that: The structural formula of the tosyl diphenyl phosphine compound is shown in the following formula I:

2. The method for preparing a tosyl diphenyl phosphorus compound according to claim 1, characterized in that: The method comprises the following preparation steps: (1) adding diphenylphosphine chloride dropwise into water, stirring the reaction until hydrolysis is complete, and separating the product by extraction to obtain diphenylphosphine oxide; (2) adding the diphenylphosphine obtained in step (1) to an alkaline aqueous solution for reaction, adding an organic solvent for reflux dehydration after the reaction is completed, and then adding 4-toluenesulfonyl chloride and an organic solvent for stirring and reaction after the dehydration is completed. After the reaction is completed, adding water and layering, taking the organic phase, drying and removing the solvent, and obtaining a toluenesulfonyl diphenylphosphine compound.

3. The method for preparing a tosyl diphenyl phosphorus compound according to claim 2, characterized in that: The temperature of the dropping process in step (1) is controlled to be below 40°C.

4. The method for preparing a tosyl diphenyl phosphorus compound according to claim 2, characterized in that: The stirring reaction in step (1) is carried out at room temperature, and the stirring reaction time is 2 to 4 hours.

5. The method for preparing a tosyl diphenyl phosphorus compound according to claim 2, characterized in that: The extraction and separation step in step (1) is as follows: adding dichloroethane to the reaction system for multiple extractions and separations, taking the organic phase, drying and concentrating it, and obtaining a diphenylphosphine mother liquor.

6. The method for preparing a tosyl diphenyl phosphine compound according to claim 2, characterized in that: The molar ratio of the diphenylphosphine chloride in step (1) to the 4-toluenesulfonyl chloride in step (2) is 0.9-1.1:

1.

7. The method for preparing a tosyl diphenyl phosphine compound according to claim 2, characterized in that: The alkaline aqueous solution in step (2) is a NaOH solution or a KOH solution with a mass concentration of 20% to 30%.

8. The method for preparing a tosyl diphenyl phosphine compound according to claim 2, characterized in that: The organic solvent in step (2) is toluene.

9. The method for preparing a tosyl diphenyl phosphine compound according to claim 2, characterized in that: The stirring reaction temperature in step (2) is 30-40° C., and the stirring reaction time is 3-6 hours.

10. Use of the tosyl diphenyl phosphine compound according to claim 1 as an ultraviolet light initiator.

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