Liquid chromatography determination method for content of iodonium tetraphenylborate photoinitiator

Abstract

According to the liquid chromatography determination method for the content of the iodonium tetraphenylborate photoinitiator, the content of the finished product iodonium tetraphenylborate photoinitiator can be directly detected, the method is used for controlling the product quality and initiation efficiency of the iodonium tetraphenylborate photoinitiator, and the method is easy to operate, high in analysis speed and accurate and reliable in result.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of analytical techniques, and particularly relates to a method for determining the content of iodonium tetraphenylborate photoinitiator by liquid chromatography. BACKGROUND

[0002] Cationic photocuring technology is a high-efficiency, energy-saving, environmentally friendly and high-quality material surface treatment technology. Cationic photocuring materials are mainly composed of resin, reactive diluent and cationic photoinitiator, among which the cationic photoinitiator is an important component. Cationic photoinitiators are widely used in adhesives, inks, coatings, sealing materials, food packaging, rapid prototyping, photoresists, computer direct plate making and other fields.

[0003] Cationic photoinitiators can absorb radiation energy, undergo transition, and produce cations that can initiate polymerization, i.e. superacids. The weaker the nucleophilicity of the anion, the stronger the acidity of the superacid produced, and the higher the efficiency of the initiation. Patent CN114805048 A provides a cationic initiator that can effectively solve the problems of surface migration and residue of onium salt initiators in the imaging layer in the prior art, and can improve the performance of processless thermal plates, especially processless thermal plates containing discrete particles; Patent CN114685698 A invents a more efficient cationic initiator, which reduces the amount of initiator, thereby avoiding or greatly reducing crystal formation, and more effectively improving the digital imaging speed, printing resistance and other properties of negative working plate making lithographic printing plates.

[0004] The quality of the initiator has a crucial impact on the performance of the plate material, but during the preparation of the photoinitiator, various by-products are produced, and the content and impurities have a significant impact on the activity of the initiator, which in turn affects the initiation efficiency of the initiator and causes a series of problems. In order to ensure the activity and initiation efficiency of the initiator, and not to have adverse effects on the system, the content of the initiator must be accurately and quickly detected, and stable initiator quality is of great significance for controlling the stability of the entire system quality and product performance. It is necessary to establish a detection method for the content of the initiator. At present, some scholars have used liquid chromatography to detect cationic photoinitiators, for example, patent CN115586293 A discloses a quality control method for the production process of triphenylsulfonium camphorsulfonate, which uses suppressive conductivity ion chromatography to detect anions such as camphorsulfonate ions, fluoride ions, chloride ions, nitrite ions, nitrate ions, sulfate ions, etc. in the production process of cationic photoinitiator triphenylsulfonium camphorsulfonate. This method mainly detects anions in the production process of cationic photoinitiators to control the quality of cations. This method is not intuitive and cannot directly reflect the quality of the photoinitiator product. SUMMARY

[0005] To solve the above problems, the application provides a liquid chromatography determination method for iodine tetraphenylborate photoinitiator content, which can directly detect the content of finished iodine tetraphenylborate photoinitiator, and is used for controlling the product quality and initiation efficiency of iodine tetraphenylborate photoinitiator.

[0006] The application is achieved in the following manner: a liquid chromatography determination method for iodine tetraphenylborate photoinitiator content, the structural formula of the iodine tetraphenylborate photoinitiator is as follows: , The mobile phase is acetonitrile-sodium trifluoroacetate aqueous solution, the volume ratio of acetonitrile and water is (50 / 50)-(90 / 10), the addition ratio of sodium trifluoroacetate in the mobile phase is 20-40 mmol / L, and isocratic elution is adopted; the chromatographic column is a C18 column, the column temperature is 25-40 DEG C, and the injection amount is 10-40 uL.

[0007] The C18 column is one of a Shim-pack GIST C18, a Diamonsil Plus C18 or a ZORBAX SB-C18 chromatographic column.

[0008] The flow rate of the mobile phase is 0.7-1.0 mL / min.

[0009] The detection wavelength used is 210-290 nm.

[0010] The liquid chromatography determination method for iodine tetraphenylborate photoinitiator content comprises the following steps, (1) Preparation of sample solution: 0.01 g of sample is weighed in a stoppered triangular flask, 7 mL of acetonitrile is first added for dissolution, and then 3 mL of water is added for dissolution; then the sample solution is diluted with a mobile phase to 0.1 mg / mL, and is filtered with a microporous filter for standby use; Preparation of control sample solution: 0.01 g of control sample is weighed in a stoppered triangular flask, 7 mL of acetonitrile is first added for dissolution, and then 3 mL of water is added for dissolution; then the sample solution is diluted with a mobile phase to 0.1 mg / mL, and is filtered with a microporous filter for standby use; (2) Detection of sample and control sample: Chromatographic conditions, mobile phase composition: the volume ratio of acetonitrile and water is (50 / 50)-(90 / 10), and the addition ratio of sodium trifluoroacetate in the mobile phase is 20-40 mmol / L; Chromatographic column: one of a Shim-pack GIST C18, a Diamonsil Plus C18 or a ZORBAX SB-C18; UV detection wavelength: 210 nm~290 nm; flow rate: 0.7~1.0 mL / min; column temperature: 25~40℃; injection volume: 10~40 uL; (3) Qualitative iodine tetraphenylborate photoinitiator with the retention time of the control sample, and the content of iodine tetraphenylborate photoinitiator in the sample is calculated by area normalization method.

[0011] In the step (1), the stoppered triangular flask is a 50 mL stoppered triangular flask, and the microporous filter membrane is a 0.22 μm needle type microporous filter membrane.

[0012] Compared with the prior art, the present application provides a liquid chromatography method for determining the content of iodine tetraphenylborate photoinitiator, which can directly detect the content of finished iodine tetraphenylborate photoinitiator, is used for quality control of iodine tetraphenylborate photoinitiator product, controls the amount of initiator in the photosensitive layer of the version material and its initiation efficiency, and has the advantages of simple operation, low cost, fast analysis speed, and accurate and reliable results. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is a chromatogram comparison diagram of the photoinitiator control sample and the sample in Example 1.

[0014] Figure 2 is a chromatogram comparison diagram of the photoinitiator control sample and the sample in Example 2.

[0015] Figure 3 is a chromatogram comparison diagram of the photoinitiator control sample and the sample in Example 3.

[0016] Figure 4 is a chromatogram comparison diagram of the photoinitiator control sample and the sample in Example 4. Figure 5 is a chromatogram comparison diagram of the photoinitiator control sample and the sample in Example 5. DETAILED DESCRIPTION

[0017] A liquid chromatography method for determining the content of iodine tetraphenylborate photoinitiator, the structural formula of the iodine tetraphenylborate photoinitiator is as follows: , The mobile phase is acetonitrile-sodium trifluoroacetate aqueous solution, the volume ratio of acetonitrile and water is (50 / 50)~(90 / 10), the addition ratio of sodium trifluoroacetate in the mobile phase is 20~40 mmol / L, and isocratic elution; the chromatographic column is a C18 column, the column temperature is 25~40℃, and the injection volume is 10~40 uL.

[0018] The C18 column is one of Shim-pack GIST C18, Diamonsil Plus C18 or ZORBAX SB-C18 chromatographic column.

[0019] The flow rate of the mobile phase is 0.7-1.0 mL / min.

[0020] The detection wavelength used is 210-290 nm.

[0021] The method for determining the content of iodonium tetraphenylborate photoinitiator by liquid chromatography comprises the following steps, (1) Preparation of sample solution: weigh 0.01 g of sample into a stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve; then dilute to 0.1 mg / mL of sample solution with mobile phase, filter with a microporous filter membrane, and reserve for use; Preparation of control sample solution: weigh 0.01 g of control sample into a stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve; then dilute to 0.1 mg / mL of sample solution with mobile phase, filter with a microporous filter membrane, and reserve for use; (2) Sample and control sample detection: Chromatographic conditions: composition of mobile phase: volume ratio of acetonitrile and water is (50 / 50)-(90 / 10), and the addition ratio of sodium trifluoroacetate in the mobile phase is 20-40 mmol / L; Chromatographic column: one of Shim-pack GIST C18, Diamonsil Plus C18 or ZORBAX SB-C18; UV detection wavelength: 210 nm-290 nm; flow rate: 0.7-1.0 mL / min; column temperature: 25-40 °C; injection volume: 10-40 uL; (3) Qualify iodonium tetraphenylborate photoinitiator by the retention time of the control sample through the chromatographic workstation, and calculate the content of iodonium tetraphenylborate photoinitiator in the sample by area normalization method.

[0022] In step (1), the stoppered flask is a 50 mL stoppered flask, and the microporous filter membrane is a 0.22 μm needle-type microporous filter membrane.

[0023] The present application will be described in detail below in conjunction with specific examples. It is necessary to point out here that the examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Those skilled in the art can make some non-essential improvements and adjustments according to the content of the present application.

[0024] Instrument and reagent sources: Chromatographic system: Shimadzu LC-20AT infusion pump, SPD-20A detector, LabSolutions workstation; Reagent: acetonitrile (chromatographic purity); Sodium trifluoroacetate (Aldrich, 97%); Photoinitiator control sample (KAYAK Research Institute).

[0025] Example 1 A liquid chromatography method for determining the content of iodonium tetraphenylborate photoinitiator in a negative working processless plate, comprising the following steps: (1) Preparation of sample solution: weigh 0.01 g of sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water; then dilute to 0.1 mg / mL with mobile phase, filter with a 0.22 μm needle-type microporous filter and reserve; Preparation of control sample solution: weigh 0.01 g of control sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water; then dilute to 0.1 mg / mL with mobile phase, filter with a microporous filter and reserve; (2) Sample and control sample detection: Chromatographic conditions, mobile phase composition: acetonitrile / (20 mmol / L) sodium trifluoroacetate aqueous solution = 50 / 50 (by volume); chromatographic column: Diamonsil Plus C18 chromatographic column, length 150 mm, particle size 3 um; UV detection wavelength: 210 nm; flow rate: 0.7 mL / min; column temperature: 25 °C; injection volume: 10 uL; Qualify iodonium tetraphenylborate photoinitiator by the retention time of the control sample through the LabSolutions workstation, and calculate the content of iodonium tetraphenylborate photoinitiator in the sample as 93.39% by area normalization method, and the chromatogram is shown in Figure Figure 1 .

[0026] Example 2: A liquid chromatography method for determining the content of iodonium tetraphenylborate photoinitiator in a negative working processless plate, comprising the following steps: (1) Preparation of sample solution: weigh 0.01 g of sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water; then dilute to 0.1 mg / mL with mobile phase, filter with a 0.22 μm needle-type microporous filter and reserve; the dilution process is: first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water, and then dilute to 0.1 mg / mL with mobile phase; Preparation of control sample solution: weigh 0.01 g of control sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water; then dilute to 0.1 mg / mL with mobile phase, filter with a microporous filter and reserve; (2) Sample and control sample detection: chromatographic conditions, mobile phase composition: acetonitrile / (25 mmol / L) sodium trifluoroacetate aqueous solution = 60 / 40 (volume ratio); chromatographic column: Shim-pack GIST chromatographic column, length 250 mm, particle size 5 um; ultraviolet detection wavelength: 230 nm; flow rate: 0.8 mL / min; column temperature: 30 ℃; injection volume: 20 uL; The content of iodonium tetraphenylborate photoinitiator in the five samples was calculated by LabSolutions workstation using the retention time of the control sample to qualitatively determine the iodonium tetraphenylborate photoinitiator, and the content and retention time data of the five samples are shown in Table 1. The comparative chromatograms of the control sample and the five samples are shown in the accompanying Figure 2 .

[0027] Table 1 Precision and repeatability data of content and retention time of five samples The data results show that the RSD of the retention time and content of the five samples is less than 1.0%, indicating that the method has good repeatability and high precision, and can meet the analysis needs.

[0028] Example 3: A liquid chromatographic method for determining the content of iodonium tetraphenylborate photoinitiator for negative working processless plate, comprising the following steps: (1) Preparation of sample solution: weigh 0.01 g of sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water, and then dilute with mobile phase to 0.1 mg / mL of sample solution. Filter with a 0.22 um needle type microporous filter and reserve; Preparation of control sample solution: weigh 0.01 g of control sample into a 50 mL stoppered flask, first dissolve in 7 mL of acetonitrile, then dissolve in 3 mL of water, and then dilute with mobile phase to 0.1 mg / mL of sample solution. Filter with a microporous filter and reserve; (2) Sample and control sample detection: chromatographic conditions, mobile phase composition: acetonitrile / (30 mmol / L) sodium trifluoroacetate aqueous solution = 70 / 30 (volume ratio); chromatographic column: ZORBAX SB-C18, length 250 mm, particle size 5 um; ultraviolet detection wavelength: 250 nm; flow rate: 0.9 mL / min; column temperature: 35 ℃; injection volume: 30 uL; The content of iodonium tetraphenylborate photoinitiator in the sample was calculated by LabSolutions workstation using the retention time of the control sample to qualitatively determine the iodonium tetraphenylborate photoinitiator, and the chromatogram is shown in the accompanying Figure 3 .

[0029] Example 4: A liquid chromatography method for determining the content of iodonium tetraphenylborate photoinitiator in negative working processless plate, comprising the following steps: (1) Preparation of sample solution: weigh 0.01 g of sample into a 50 mL stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve, and finally dilute with mobile phase to 0.1 mg / mL of sample solution, filter with a 0.22 μm needle type microporous filter and reserve; Preparation of control sample solution: weigh 0.01 g of control sample into a 50 mL stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve, and finally dilute with mobile phase to 0.1 mg / mL of sample solution, filter with a microporous filter and reserve; (2) Sample and control sample detection: chromatographic conditions, mobile phase composition: acetonitrile / (35 mmol / L) sodium trifluoroacetate aqueous solution = 80 / 20 (volume ratio); chromatographic column: ZORBAX SB-C18, length 150 mm, particle size 3.5 um; UV detection wavelength: 270 nm; flow rate: 1.0 mL / min; column temperature: 40 °C; injection volume: 40 uL; Qualify iodonium tetraphenylborate photoinitiator by the retention time of the control sample through the LabSolutions workstation, and calculate the content of iodonium tetraphenylborate photoinitiator in the sample as 85.87% by area normalization method, and the chromatogram is shown in Figure Figure 4 .

[0030] Example 5: A liquid chromatography method for determining the content of iodonium tetraphenylborate photoinitiator in negative working processless plate, comprising the following steps: (1) Preparation of sample solution: weigh 0.01 g of sample into a 50 mL stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve, and finally dilute with mobile phase to 0.1 mg / mL of sample solution, filter with a 0.22 μm needle type microporous filter and reserve; Preparation of control sample solution: weigh 0.01 g of control sample into a 50 mL stoppered flask, first add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve, and finally dilute with mobile phase to 0.1 mg / mL of sample solution, filter with a microporous filter and reserve; (2) Sample and control sample detection: chromatographic conditions, mobile phase composition: acetonitrile / (40 mmol / L) sodium trifluoroacetate aqueous solution = 90 / 10 (volume ratio); chromatographic column: Diamonsil Plus C18, length 250 mm, particle size 5 um; ultraviolet detection wavelength: 290 nm; flow rate: 0.7 mL / min; column temperature: 35 DEG C; injection volume: 20 uL; The content of iodonium tetraphenylborate photoinitiator in the sample was calculated as 80.29% by area normalization method through the LabSolutions workstation, and the chromatogram is shown in the following figure: Figure 5 .

[0031] The above only describes the preferred embodiments of the present application, but the protection scope of the present application is not limited thereto. It should be noted that, for those skilled in the art and any person skilled in the art, under the premise of not departing from the overall concept of the present application, according to the technical scheme and inventive concept of the present application, equivalent replacement or change, and several changes and improvements made, these should also be regarded as the protection scope of the present application.

Claims

1. A liquid chromatography method for determining the content of iodonium tetraphenylborate photoinitiator, characterized in that: The structural formula of the iodonium tetraphenylborate photoinitiator is as follows: ， The mobile phase was an aqueous solution of acetonitrile and sodium trifluoroacetate, with a volume ratio of acetonitrile to water of 50:50-90:

10. The sodium trifluoroacetate concentration in the mobile phase was 20-40 mmol / L, and isocratic elution was performed. A C18 column was used, with a column temperature of 25℃-40℃ and an injection volume of 10-40 μL.

2. The method for determining the content of iodonium tetraphenylborate photoinitiator according to claim 1, characterized in that: The C18 column is one of the following: Shim-pack GIST C18, Diamonsil Plus C18, or ZORBAX SB-C18 column.

3. The method for determining the content of iodonium tetraphenylborate photoinitiator according to claim 1, characterized in that: The flow rate of the mobile phase is 0.7–1.0 mL / min.

4. The method for determining the content of iodonium tetraphenylborate photoinitiator according to claim 1, characterized in that: The detection wavelength used is 210–290 nm.

5. The method for determining the content of iodonium tetraphenylborate photoinitiator according to any one of claims 1-4, characterized in that: Includes the following steps, (1) Preparation of sample solution: Weigh 0.01 g of sample into a stoppered Erlenmeyer flask, add 7 mL of acetonitrile to dissolve, then add 3 mL of water to dissolve; then dilute with the mobile phase to a sample solution of 0.1 mg / mL, filter with a microporous membrane and set aside. Preparation of the control sample solution: Weigh 0.01 g of the control sample into a stoppered Erlenmeyer flask, add 7 mL of acetonitrile to dissolve it, then add 3 mL of water to dissolve it; then dilute it with the mobile phase to a sample solution of 0.1 mg / mL, filter it through a microporous membrane and set it aside for later use. (2) Detection of sample and control samples: Chromatographic conditions, mobile phase composition: acetonitrile to water volume ratio of (50 / 50) to (90 / 10), sodium trifluoroacetate added to the mobile phase at a ratio of 20 to 40 mmol / L; Chromatographic column: One of Shim-pack GIST C18, Diamonsil Plus C18 or ZORBAX SB-C18; UV detection wavelength: 210 nm~290 nm; flow rate: 0.7~1.0 mL / min; column temperature: 25℃~40℃; injection volume: 10~40 uL; (3) The retention time of the control sample was used to qualitatively identify the iodonium tetraphenylborate photoinitiator, and the content of iodonium tetraphenylborate photoinitiator in the sample was calculated by the area normalization method.

6. The method for determining the content of iodonium tetraphenylborate photoinitiator according to claim 5, characterized in that: In step (1), the stoppered triangular bottle is a 50 mL stoppered triangular bottle, and the microporous filter membrane is a 0.22 μm needle-type microporous filter membrane.

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