CN102879494A - High performance liquid chromatography quantitative determination method of boric acid in water-based adhesive - Google Patents

Abstract

The invention discloses a high performance liquid chromatography quantitative determination method of boric acid in a water-based adhesive. The method comprises the following steps: (1) weighing a water-based adhesive sample, adding water, dissolving in a triangular flask to obtain a solution, then performing ultrasonic vibration and centrifugation; (2) adding the supernatant liquor of the solution into a triangular flask, adding a developer solution into the triangular flask, well mixing, drying by distillation in a water-bath kettle; adding a solvent, transferring the solution into a volumetric flask, diluting with the solvent to reach the scale, well mixing; (3) analyzing the solution by a high performance liquid chromatograph; (4) performing quantification by an external standard method with the relation that the peak area is proportional to the concentration. The method adds a curcumin-oxalic acid developer into the sample after dilution, ultrasonic vibration and centrifugation, and puts the sample in a constant-temperature water bath in a water-bath kettle. The solid obtained after drying by distillation is dissolved by the solvent and reaches a constant volume in the volumetric flask. The peak area of a boron-curcumin complex is determined by high performance liquid chromatography, and the boric acid content is calculated by comparison with a standard curve. The method is rapid, reliable, simple and practical.

Description

A kind of high performance liquid chromatography quantitative determination method of boric acid in water-based glue

technical field

The invention relates to a high-performance liquid chromatography quantitative determination method for boric acid in water-based glue.

Background technique

Boric acid is a white crystalline powder or colorless scales with pearly luster, which is irritating and can be used as a chemical reagent and to produce insecticides for cockroaches and beetles, and as a hemostatic and antiseptic in medicine. Borax can react with stomach acid to produce boric acid after being ingested through food. Boric acid is not allowed as a food additive, but folks often use borax or boric acid as an insecticide and preservative in grains. In the early years, there was also the problem of using boric acid as a food preservative and leavening agent. For boric acid in latex, there are generally two ways to store latex, one is high-ammonia storage, and the other is low-ammonia storage with boric acid with a content between 0.2-0.25%.

High-performance liquid chromatography is a modern chromatographic analysis method developed on the basis of classical liquid chromatography in the late 1960s. There have been different names in history, such as high-pressure liquid chromatography, high-speed liquid chromatography and High Resolution Liquid Chromatography. In terms of separation principle, high-performance liquid chromatography adopts high-pressure infusion pump, high-efficiency particle stationary phase and high-sensitivity detector. High-performance liquid chromatography has the advantages of fast analysis speed, good separation efficiency, high detection sensitivity, fast analysis speed and convenient sample recovery. And the advantages of high degree of operation automation. This method has been widely used in the fields of bioengineering, pharmaceutical industry, food industry, environmental monitoring and petrochemical industry.

At present, there are some reports on the determination of boric acid by high performance liquid chromatography in China.

In 2002, Sui Yingjun and others reported the determination of the content of borax in ice boron powder by high performance liquid chromatography. A HPLC method was established for the determination of borax in Bingborax powder. Results Borax had a good linear relationship in the range of 0.14-0.71 μg·m] ^-1 injection volume, r = 0.9992. Conclusion The method for content determination is simple, accurate and reproducible.

In 2007, Chen Yan et al. reported the reversed-phase high-performance liquid chromatography determination method of borax in food. A reverse-phase high-performance liquid chromatography (RP-HPLC) method for the determination of borax in food was established. The detection limit of the method was 6.4ng/kg, the RSD was 2.3%, the recovery rate was 90.63%-96.88%, and the linear range was 0.032-0.32 μg/L, the correlation coefficient is 0.9992.

In 1995, Hu Qizhi and others reported the research and application of high performance liquid chromatography of boron-curcumin complex. The complex compound formed by boron and protonated curcumin in non-aqueous system was studied with anhydrous methanol as solvent, and methanol-water (80:20V/V) was used as mobile phase (1.00mL/min) on C18 chromatographic column. ) separation and detection. The linear range of the calibration curve of boron is 0.4-3.2 μg/25mL, and the calibration limit of boron is 0.08ng. This method is used for the analysis of compound boron fertilizer, and the result is satisfactory.

The pretreatment methods of these methods mostly adopt the method of protonation of concentrated sulfuric acid mixed acid to process and then enter the high-performance liquid chromatography for determination, however. Concentrated sulfuric acid is dangerous to the operator, and it is easy to cause corrosion to instruments and equipment.

At present, there are few reports in the literature on the determination method of boric acid in water-based adhesives, but this determination method is safe, easy and will not cause damage to equipment. For the determination of boric acid content in water-based glue, it has the advantages of good reproducibility and strong operability.

Contents of the invention

The invention discloses a method for determining boric acid in water-based glue by high-performance liquid chromatography. It is characterized in that the method comprises the following steps:

(1) Take the water-based glue sample, add water and dissolve it in a conical flask to obtain a solution, then ultrasonically vibrate and centrifuge;

(2) Take the supernatant of the above solution and add it to the Erlenmeyer flask, add the developer solution in the Erlenmeyer flask, mix well and evaporate to dryness on the water bath; add the solvent and transfer it to the volumetric flask, dilute to the mark with solvent, mix uniform;

(3) solution liquid is analyzed by high performance liquid chromatography;

(4) Quantify with the external standard method using the relationship between the peak area and the concentration.

The weight of the water-based glue sample in the step (1) is 0.1-2g; the volume of water added is 10-1000mL, the ultrasonic oscillation time is 10-30min; the centrifuge speed is 4000-12000 rpm; the centrifugation time is 5-30min .

In the step (2), 0.1-2 mL of the supernatant liquid of the solution is taken; the color developer solution is curcumin oxalic acid solution, and the amount of the color developer is 2-8 mL.

The temperature of the water bath in the step (2) is 30-60 degrees, and the volume of the volumetric flask is 20-100mL.

The solvent in the step (2) is any one of methanol, 95% ethanol or absolute ethanol.

The chromatographic column in the step (3) adopts a reverse-phase chromatographic column, the mobile phase ratio: methanol: water = 10-90: 90-10, the column temperature of the chromatographic column: 20-35 ° C; the flow rate of the high-performance liquid chromatography is controlled at 0.2 ~ 1mL /min; detection by ultraviolet detector, detection wavelength: 500-600nm.

Compared with the prior art, the beneficial effects of the present invention are: the determination steps of the method are to add curcumin-oxalic acid chromogen to the centrifuged sample after dilution, ultrasonication and constant temperature water bath on the water bath. The solid obtained after evaporating to dryness was dissolved in a solvent and fixed to volume in a volumetric flask. The peak area of boron-curcumin complex was determined by high performance liquid chromatography, and the content of boric acid was calculated according to the standard curve. This method is fast, reliable, simple and easy to implement.

Detailed ways

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. The examples are only to help the understanding of the present invention, and should not be regarded as specific limitations on the present invention.

(1) Pretreatment of samples

Accurately weigh 1g of water-based glue sample, add 50mL of water to dissolve in a 100mL Erlenmeyer flask, ultrasonically oscillate for 10min, and centrifuge for 10min. Take 3mL of the supernatant and add it into the Erlenmeyer flask,

(2) Solution preparation

After diluting the above clear solution five times, add the developer solution into the Erlenmeyer flask, mix well, evaporate to dryness on a 55°C water bath, add ethanol, transfer to a 25mL volumetric flask, dilute to the mark with ethanol, and mix well.

(2) The solution liquid is analyzed by high performance liquid chromatography.

According to the method determined in the present invention, the above solution is filtered through a 0.45 μm microporous membrane and then injected into a liquid chromatograph, and the chromatographic conditions are selected for measurement to obtain the content of boric acid in the water-based glue.

Example 1

Prepare boric acid standard solution according to the method described above, inject the liquid chromatograph after the standard solution obtained above is filtered through a 0.45 μm microporous membrane, and measure under the chromatographic conditions described below according to the method determined in the present invention.

The results showed that the peaks were good, and the chromatographic peaks of boric acid were completely separated from the chromatographic peaks of other components.

Among them, chromatographic column: Extend-C18; mobile phase: methanol: water (90:10 volume ratio); chromatographic column temperature: 25 ° C; injection volume: 5 μ L; flow rate: 1 mL/min; detector: ultraviolet detector; Wavelength: 550nm.

Example 2

Prepare the water-based glue sample solution according to the method described above, filter the standard solution obtained above through a 0.45 μm microporous membrane, and inject it into a liquid chromatograph, and carry out under the chromatographic conditions described below according to the method determined in the present invention Determination.

The results showed that the peaks were good, and the chromatographic peaks of boric acid were completely separated from the chromatographic peaks of other components.

Among them, chromatographic column: Rx-C18; mobile phase: methanol: water (80:20 volume ratio); chromatographic column temperature: 35 ° C; injection volume: 10 μ L; flow rate: 0.8 mL/min; detector: ultraviolet detector; Detection wavelength: 550nm.

Example 3

Weigh 0.5g of water-based glue sample, add 50mL of water to dissolve it in a 100mL Erlenmeyer flask, ultrasonicate for 5min, and centrifuge for 5min in a centrifuge. Get 2mL of the supernatant and add it to the Erlenmeyer flask, filter the solution obtained above through a 0.45 μm microporous membrane and inject it into a liquid chromatograph, and measure it under the chromatographic conditions described below according to the method determined in the present invention.

The results showed that the peaks were good, and the chromatographic peaks of boric acid were completely separated from the chromatographic peaks of other components.

Among them, chromatographic column: Eclipse XDB; mobile phase: methanol: water (85:15 volume ratio); chromatographic column temperature: 30°C; injection volume: 20μL; flow rate: 0.7mL/min; detector: ultraviolet detector; Detection wavelength: 550nm.

Example 4

Weigh 1g of water-based glue sample, add 100mL of water to dissolve in a 250mL Erlenmeyer flask, shake for 15min, and centrifuge for 15min in a centrifuge. Get 0.5mL supernatant liquid and add in the Erlenmeyer flask, the solution obtained above is injected into the liquid chromatograph after filtering through the 0.45 μm microporous membrane, and measure under the chromatographic conditions described below according to the method determined in the present invention.

The results showed that the peaks were good, and the chromatographic peaks of boric acid were completely separated from the chromatographic peaks of other components.

Among them, chromatographic column: Eclipse Plus; mobile phase: methanol: water (75:15 volume ratio); chromatographic column temperature: 30°C; injection volume: 10μL; flow rate: 0.85mL/min; detector: ultraviolet detector; Detection wavelength: 550nm.

Example 5

Weigh 2g of water-based glue sample, add 150mL of water to dissolve it in a 250mL Erlenmeyer flask, ultrasonicate for 15min, and centrifuge for 20min in a centrifuge. Get 1mL supernatant liquid and add in the Erlenmeyer flask, prepare water-based glue sample solution according to the method described above, inject the liquid chromatograph after the standard solution obtained above is filtered through 0.45 μm microporous membrane, according to the method determined in the present invention , determined under the chromatographic conditions described below.

The results showed that the peaks were good, and the chromatographic peaks of boric acid were completely separated from the chromatographic peaks of other components.

Among them, chromatographic column: ZORBAX ODS; mobile phase: methanol: water (50:50 volume ratio); chromatographic column temperature: 25 ℃; injection volume: 15μL; flow rate: 0.2mL/min; Wavelength: 550nm.

Claims (6)

1. the high performance liquid chromatography method for quantitatively determining of a water base adhesive mesoboric acid is characterized in that the method may further comprise the steps:

(1) take by weighing the water base adhesive sample, adding water is dissolved in and obtains solution in the triangular flask, then ultrasonic or vibration, centrifugal;

(2) get in the supernatant liquor adding triangular flask of mentioned solution, in triangular flask, add chromogenic reagent solution, mix afterwards evaporate to dryness on water-bath; Add solvent and be transferred in the volumetric flask, with solvent dilution to scale, mixing;

(3) solution liquid adopts high performance liquid chromatograph to analyze;

(4) adopt the relation of peak area and concentration direct ratio quantitative with external standard method.

2. the high performance liquid chromatography method for quantitatively determining of water base adhesive mesoboric acid according to claim 1, it is characterized in that: the sample weighting amount of the water base adhesive sample of described step (1) is 0.1-2g; The volume that adds entry is 10-1000mL, ultrasonic or duration of oscillation 10-30min; Centrifuge speed 4000-12000 turns; Centrifugation time is 5-30min.

3. the high performance liquid chromatography method for quantitatively determining of water base adhesive mesoboric acid according to claim 1 is characterized in that, the middle solution of described step (2) at the middle and upper levels clear liquid is got 0.1-2mL; Chromogenic reagent solution is the curcumin oxalic acid solution, and the consumption of developer is 2-8mL.

4. the high performance liquid chromatography method for quantitatively determining of water base adhesive mesoboric acid according to claim 1 is characterized in that, described step (2) water-bath temperature is the 30-60 degree, and the volumetric flask volume is 20-100mL.

5. the high performance liquid chromatography method for quantitatively determining of water base adhesive mesoboric acid according to claim 1 is characterized in that, in the described step (2) solvent be in methyl alcohol, 95% ethanol or the absolute ethyl alcohol any one.

6. the high performance liquid chromatography method for quantitatively determining of water base adhesive mesoboric acid according to claim 1, it is characterized in that, described step (3) chromatographic column adopting reverse-phase chromatographic column, mobile phase ratio: methyl alcohol: water=10-90: 90-10, chromatographic column column temperature: 20-35 ℃; The high performance liquid chromatography coutroi velocity is at 0.2～1mL/min; The employing UV-detector detects, and detects wavelength: 500-600nm.