A method for determining the content of (4-tert-butylphenyl) diphenyl phosphate in hydraulic oil, lubricant, grease
By using hexane:dichloromethane solvent extraction and GC-MS determination, the problem of rapid and accurate determination of (4-tert-butylphenyl)diphenyl thiophosphate content in hydraulic oil, lubricants, and greases was solved, achieving a low detection limit of 50 mg/kg.
Patent Information
- Application Number
- CN202610520248.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-20
- Publication Date
- 2026-07-10
AI Technical Summary
Existing technologies cannot quickly and accurately determine the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oils, lubricants, and greases, and there is a lack of effective detection methods.
The sample was extracted with a 1:1 solvent of hexane and dichloromethane, and the concentration of (4-tert-butylphenyl)diphenyl thiophosphate was determined by gas chromatography-mass spectrometry (GC-MS). The content was calculated by external standard method.
A rapid, simple, and accurate method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate was developed, with a minimum quantitative concentration of 50 mg/kg, meeting the monitoring requirements.
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Figure CN122361658A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of analytical chemistry, specifically a method for determining one of the reactants of triphenyl thiophosphate and tert-butylated phenyl derivatives in hydraulic oil, lubricant, and grease: (4-tert-butylphenyl)diphenyl thiophosphate. Background Technology
[0002] Triphenyl thiophosphate and its tert-butylated phenyl derivatives exhibit biotoxicity and reproductive toxicity with long-term persistent effects. This substance is primarily used in hydraulic fluids, lubricants, and greases. Other potential releases into the environment may occur from: minimal releases in indoor closed systems (e.g., coolant in refrigerators, oil-based electric heaters); and minimal releases in outdoor closed systems (e.g., hydraulic fluids in automotive suspensions, lubricating oils in engine oils, and brake fluids).
[0003] (4-tert-butylphenyl)diphenyl thiophosphate, with the molecular formula C22H23O3PS, belongs to the triphenyl thiophosphate and tert-butylphenyl derivatives. Due to the diversity of its derivatives, no single derivative is currently available on the market. The only way to detect this substance is through preliminary screening using O,O,O-triphenyl thiophosphate (CAS 597-82-0). Therefore, it is urgent to establish a method for the synthesis and detection of (4-tert-butylphenyl)diphenyl thiophosphate.
[0004] (4-tert-butylphenyl)diphenyl thiophosphate structural formula:
[0005] Triphenyl thiophosphate and tert-butylated phenyl derivatives: Summary of the Invention
[0006] The purpose of this invention is to overcome the above-mentioned shortcomings and provide a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oil, lubricant, and grease. This method is not only fast and simple, but also enables accurate determination of the content of (4-tert-butylphenyl)diphenyl thiophosphate, thus solving the problem of determining the content of (4-tert-butylphenyl)diphenyl thiophosphate.
[0007] To achieve the above objective, a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oil, lubricant, and grease is designed, comprising the following steps: 1) Sample pretreatment: Mix the liquid sample thoroughly and set aside; 2) Sample extraction: The pretreated sample was extracted by ultrasonic extraction using a 1:1 solvent of hexane and dichloromethane; 3) The concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 2) was determined by GC-MS gas chromatography-mass spectrometry; 4) Based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 3), calculate the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample.
[0008] Further, in step 2), weigh an appropriate amount of sample into a 20 mL headspace vial, add an appropriate amount of hexane:dichloromethane solvent in a 1:1 ratio, and sonicate extract for 60 min in a water bath at 50°C±5°C. Remove the vial, allow it to cool naturally to room temperature, filter it into a sample vial, and it is ready for testing.
[0009] Further, in step 2), 10 mL of hexane: dichloromethane in a 1:1 solvent ratio is measured, 1 g of sample is weighed into a 20 mL headspace vial, the cap is closed and mixed well to ensure complete dispersion of the sample, and then ultrasonically extracted in a water bath at 50°C±5°C.
[0010] Furthermore, the preparation steps of the (4-tert-butylphenyl)diphenyl thiophosphate standard solution of the present invention are as follows: (1) Weigh 10 mg of (4-tert-butylphenyl) diphenyl thiophosphate standard, add 10 mL of hexane: dichloromethane in a 1:1 ratio and mix well to prepare a 1000 mg / L (4-tert-butylphenyl) diphenyl thiophosphate standard stock solution. (2) Measure 1 mL of the stock solution into a 10 mL volumetric flask and dilute to the mark with n-hexane:dichloromethane as a 1:1 solvent. The concentration at this point is 100 mg / L. (3) 100 mg / L (4-tert-butylphenyl) diphenyl thiophosphate was diluted with n-hexane: dichloromethane in a 1:1 ratio to form standard curves of 5, 10, 15, 20, and 25 mg / L for instrumental analysis.
[0011] Further, in step 3), the GC-MS measurement conditions are as follows: Further, in step 4), the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample is calculated from the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the extraction solution. According to the solvent calibration curve, the external standard method is used for quantification, and the minimum quantification concentration is 50 mg / kg.
[0012] Further, in step 4), the calculation formula for (4-tert-butylphenyl)diphenyl thiophosphate is: X = C × V × DF / m in, X: (4-tert-butylphenyl)diphenyl thiophosphate content in the sample (mg / kg); C: Sample concentration (mg / L) obtained from the standard curve; V: Final volume (mL); m: Sample mass (g); DF: Dilution factor.
[0013] Compared with the prior art, the present invention has the following advantages: (1) This invention is a method for extracting (4-tert-butylphenyl)diphenyl thiophosphate using organic solvents and determining its content by GC-MS; (2) This invention is not only fast and simple to determine, but also can accurately determine the content of (4-tert-butylphenyl)diphenyl thiophosphate, with a minimum quantitative concentration of 50 mg / kg; (3) The present invention solves the problem of the method for monitoring the content of (4-tert-butylphenyl)diphenyl thiophosphate and fully meets the requirements for monitoring the content of (4-tert-butylphenyl)diphenyl thiophosphate. In summary, this invention provides a method for the determination of (4-tert-butylphenyl)diphenyl thiophosphate content in hydraulic oil, lubricants, and greases by gas chromatography-mass spectrometry using a 1:1 solvent extraction of n-hexane and dichloromethane. The minimum quantitative concentration is 50 mg / kg, and this method is worthy of widespread application. Attached Figure Description
[0014] Figure 1 This is the chromatogram of (4-tert-butylphenyl)diphenyl thiophosphate of the present invention; Figure 2 This is the mass spectrum of (4-tert-butylphenyl)diphenyl thiophosphate ester of the present invention. Detailed Implementation
[0015] This invention belongs to the field of analytical chemistry. Addressing the problem of the lack of a method for detecting added content, it provides a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate, one of the reactants of triphenyl thiophosphate and tert-butylated phenyl derivatives, in hydraulic oil, lubricants, and greases by extraction with a 1:1 solvent of hexane and dichloromethane and gas chromatography-mass spectrometry (GC-MS).
[0016] The principle of this invention is as follows: (4-tert-butylphenyl)diphenyl thiophosphate in the sample is extracted with an organic solution, filtered, and then the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample is determined by GC-MS. This method is rapid, simple, and can accurately determine the content of (4-tert-butylphenyl)diphenyl thiophosphate, with a minimum quantitative concentration of 50 mg / kg.
[0017] This invention provides a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oil, lubricant, and grease, comprising the following steps: 1) Sample pretreatment: Mix the liquid sample thoroughly and set aside; 2) Sample extraction: The pretreated sample was extracted by ultrasonic extraction with a 1:1 solvent of hexane:dichloromethane. Specifically, an appropriate amount of sample was weighed into a 20mL headspace vial, an appropriate amount of a 1:1 solvent of hexane:dichloromethane was added, and the sample was ultrasonically extracted for 60 min in a water bath at 50°C±5°C. The sample was then removed, allowed to cool naturally to room temperature, filtered into a sample vial, and ready for analysis. 3) The concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 2) was determined by GC-MS gas chromatography-mass spectrometry; 4) Based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 3), calculate the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample.
[0018] Specifically, the method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oil, lubricant, and grease according to the present invention comprises the following determination steps: 1) Sample pretreatment: Mix liquid samples thoroughly; 2) Sample extraction: Measure 10 mL of a 1:1 hexane:dichloromethane solvent; weigh 1.0 g of sample into a 20 mL headspace vial, cap and mix thoroughly to ensure complete sample dispersion; extract by sonication in a water bath at 50°C±5°C for 60 min, remove, allow to cool naturally to room temperature, filter into a sample vial, and analyze using GC-MS. Preparation of (4-tert-butylphenyl)diphenyl thiophosphate standard solution: (1) Weigh 10 mg of (4-tert-butylphenyl) diphenyl thiophosphate standard, add 10 mL of n-hexane: dichloromethane 1:1 solvent and mix well to prepare a 1000 mg / L (4-tert-butylphenyl) diphenyl thiophosphate standard stock solution; (2) Measure 1 mL of the stock solution into a 10 mL volumetric flask and dilute to the mark with n-hexane:dichloromethane 1:1 solvent. The concentration at this point is 100 mg / L. (3) Dilute 100 mg / L (4-tert-butylphenyl) diphenyl thiophosphate with n-hexane: dichloromethane at a ratio of 1:1 to prepare standard curves of 5, 10, 15, 20, and 25 mg / L for instrumental analysis.
[0019] 3) The concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 2) was determined by GC-MS; the determination conditions of the gas chromatography-mass spectrometry were as follows: 4) Calculate the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 3). Specifically, the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample is obtained by converting the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the extraction solution. The content is quantified by external standard method according to the solvent calibration curve, and the minimum quantification concentration is 50 mg / kg.
[0020] Formula calculation for (4-tert-butylphenyl)diphenylthiophosphate: X = C × V × DF / m in, X: Content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample (mg / kg); C: Sample concentration (mg / L) obtained from the standard curve V: Final volume (mL); m: Sample mass (g); DF: Dilution factor.
[0021] The present invention will be further described below with reference to the accompanying drawings and specific embodiments: Example 1: Determination of the content of (4-tert-butylphenyl)diphenyl thiophosphate 1. Preparation of sample solution: Measure 10 mL of hexane:dichloromethane 1:1 solvent; weigh 1.0 g of sample into a 20 mL headspace vial, cap and mix well to ensure complete dispersion; extract by sonication in a water bath at 50°C±5°C for 60 min, remove and allow to cool naturally to room temperature, filter into a sample vial, and prepare for analysis.
[0022] 2. Set instrument parameters: 3. Qualitative and quantitative 1) Qualitative By comparing the retention times of the sample peak and the standard peak, and by comparing the mass spectrum of the sample peak and the mass spectrum of the standard substance, it can be determined whether (4-tert-butylphenyl)diphenyl thiophosphate is detected in the sample.
[0023] 2) Quantitative Quantification was performed using the external standard method based on the calibration curve.
[0024] 4. Calculation The content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample is calculated based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution.
[0025] In summary, this invention provides a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate (CAS: 1026363-94-9) in hydraulic oils, lubricants, and greases. The determination steps are as follows: 1) Mix the liquid sample thoroughly and set aside; 2) Extract the sample using a 1:1 solvent of hexane and dichloromethane via ultrasonication; 3) Analyze the sample extract obtained in step 2) using gas chromatography-mass spectrometry; 4) Calculate the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extract obtained in step 3). This invention provides a method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oils, lubricants, and greases after extraction with a 1:1 solvent of hexane and dichloromethane, using gas chromatography-mass spectrometry. This method can accurately determine the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oils, lubricants, and greases, with a minimum quantitative concentration of 50 mg / kg.
[0026] Contents not described in detail in this specification are existing technologies known to those skilled in the art and will not be elaborated upon here. This invention is not limited to the above-described embodiments; any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of this invention should be considered equivalent substitutions and are included within the scope of protection of this invention.
Claims
1. A method for determining the content of (4-tert-butylphenyl)diphenyl thiophosphate in hydraulic oil, lubricant, and grease, characterized in that, Includes the following steps: 1) Sample pretreatment: Mix the liquid sample thoroughly and set aside; 2) Sample extraction: The pretreated sample was extracted by ultrasonic extraction using a 1:1 solvent of hexane and dichloromethane; 3) The concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 2) was determined by GC-MS gas chromatography-mass spectrometry; 4) Based on the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the sample extraction solution obtained in step 3), calculate the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample.
2. The method as described in claim 1, characterized in that: In step 2), weigh an appropriate amount of sample into a 20 mL headspace vial, add an appropriate amount of hexane:dichloromethane solvent in a 1:1 ratio, and sonicate for 60 min in a water bath at 50°C±5°C. Remove the vial, allow it to cool naturally to room temperature, filter it into a sample vial, and it is ready for testing.
3. The method as described in claim 2, characterized in that: In step 2), measure 10 mL of hexane: dichloromethane as a 1:1 solvent, weigh 1 g of sample into a 20 mL headspace vial, cap and mix well to completely disperse the sample, and then ultrasonically extract in a water bath at 50°C±5°C.
4. The method as described in claim 1, characterized in that, The steps for preparing the (4-tert-butylphenyl)diphenyl thiophosphate standard solution are as follows: (1) Weigh 10 mg of (4-tert-butylphenyl) diphenyl thiophosphate standard, add 10 mL of hexane: dichloromethane in a 1:1 ratio and mix well to prepare a 1000 mg / L (4-tert-butylphenyl) diphenyl thiophosphate standard stock solution. (2) Measure 1 mL of the stock solution into a 10 mL volumetric flask and dilute to the mark with n-hexane:dichloromethane as a 1:1 solvent. The concentration at this point is 100 mg / L. (3) 100 mg / L (4-tert-butylphenyl) diphenyl thiophosphate was diluted with n-hexane: dichloromethane in a 1:1 ratio to form standard curves of 5, 10, 15, 20, and 25 mg / L for instrumental analysis.
5. The method as described in claim 1, characterized in that, In step 3), the GC-MS measurement conditions are as follows: 。 6. The method as described in claim 1, characterized in that: In step 4), the content of (4-tert-butylphenyl)diphenyl thiophosphate in the sample is calculated from the concentration of (4-tert-butylphenyl)diphenyl thiophosphate in the extraction solution. According to the solvent calibration curve, the external standard method is used for quantification, and the minimum quantification concentration is 50 mg / kg.
7. The method as described in claim 6, characterized in that, In step 4), the formula for calculating (4-tert-butylphenyl)diphenyl thiophosphate is: in, X: (4-tert-butylphenyl)diphenyl thiophosphate content in the sample (mg / kg); C: Sample concentration (mg / L) obtained from the standard curve; V: Final volume (mL); m: Sample mass (g); DF: Dilution factor.