CN109507306B - Method for determining acetyl tributyl citrate in water-based adhesive - Google Patents
Method for determining acetyl tributyl citrate in water-based adhesive Download PDFInfo
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- CN109507306B CN109507306B CN201811119680.3A CN201811119680A CN109507306B CN 109507306 B CN109507306 B CN 109507306B CN 201811119680 A CN201811119680 A CN 201811119680A CN 109507306 B CN109507306 B CN 109507306B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/04—Preparation or injection of sample to be analysed
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- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention discloses a method for measuring the content of acetyl tributyl citrate in water-based adhesive, which comprises the steps of firstly extracting acetyl tributyl citrate in a water-based adhesive sample by acetonitrile, and then adding C18Dispersing solid phase extractant, performing vortex oscillation, performing centrifugal separation, filtering the supernatant with a filter membrane, analyzing with an ultra-high performance liquid chromatograph, and quantitatively measuring the content of acetyl tributyl citrate in the solution by an external standard method. The invention provides a simple, rapid and efficient method for determining acetyl tributyl citrate in water-based adhesive, which has the following specific advantages: 1) aiming at the characteristics of small dead volume and high sensitivity of a UPLC instrument pipeline, a sample pretreatment method is developed in a targeted manner, and C is added18Bonded silica gel is used as a dispersed solid phase extracting agent, so that the interference of non-target substances in a matrix is greatly reduced; 2) according to the characteristics of the target compound, a new rapid analysis method is established by optimizing UPLC chromatographic conditions, and the determination time is less than 20 min.
Description
Technical Field
The invention belongs to the technical field of analysis, and particularly relates to a method for determining the content of acetyl tributyl citrate in a water-based adhesive.
Background
The plasticizer is a substance which can reduce the glass transition temperature and the melting temperature of a high molecular compound, improve the brittleness of an adhesive layer and improve the melt fluidity. The addition of a proper amount of plasticizer in the adhesive component can improve the shear strength and the uneven tearing strength and increase the flexibility of the adhesive film. Acetyl tributyl citrate is a new green, non-toxic plasticizer, LD50 ═ 4000mg/kg, and is useful as a plasticizer for polyvinyl chloride, cellulose resins, and synthetic rubbers. The product can be used for nontoxic PVC granulation, food packaging containers, children toy products, medical products, films, plates, cellulose coatings and other products, and can also be added in the production of water-based adhesive products.
At present, national standards or industrial standards for detecting the acetyl tributyl citrate in the adhesive do not exist in China, so that the establishment of the method for determining the acetyl tributyl citrate in the water-based adhesive has important significance for quality monitoring of water-based adhesive production enterprises and raw material monitoring of purchasing parties.
Disclosure of Invention
The invention aims to establish a simple and rapid determination method of acetyl tributyl citrate in water-based adhesive, which utilizes UPLC as an instrument analysis means and establishes a corresponding sample pretreatment method in a matching way so as to obtain a clean on-machine solution and reduce the interference of a matrix on a determination target substance.
The purpose of the invention is realized by the following technical scheme:
a method for measuring the content of acetyl tributyl citrate in water-based adhesive comprises the following steps:
step one), extracting acetyl tributyl citrate in a water-based adhesive sample by using acetonitrile, adding a C18 dispersed solid phase extracting agent, performing vortex oscillation and centrifugal separation, and filtering a supernatant by using a filter membrane to obtain a sample solution to be detected;
step two), preparing acetyl tributyl citrate standard curve solution;
step three), using an ultra-high performance liquid chromatograph and taking acetonitrile and water as mobile phases to carry out gradient elution analysis on the sample solution to be detected and the standard curve solution, and quantitatively measuring acetyl tributyl citrate by an external standard method; and calculating the content of the acetyl tributyl citrate in the water-based adhesive according to the measurement result.
In a further improvement, the chromatographic conditions in the step three) are as follows: the chromatographic column is Atlantis T3
3mm × 100 mm; gradient elution procedure: linearly increasing the ratio of acetonitrile to water from 20:80 to 100% acetonitrile for 0-15 min; 15-20 min, 100% acetonitrile;
column temperature: 20-40 ℃; flow rate: 0.3-0.6 mL/min; sample introduction amount: 1-5 mu L; the detector is a diode array detector, and the detection wavelength is 212 nm.
In a further improvement, the column temperature is 30 ℃, the flow rate is 0.6mL/min, and the sample injection amount is 2 mu L.
Further improvement, in the step one), 0.5-1 g of water-based adhesive sample is weighed and placed in a conical flask, 5-20 mL of acetonitrile solution is added, vortex oscillation is carried out for 5min, a small amount of extract liquor is taken for centrifugal separation, and then a 0.22 mu m organic filter membrane is used for filtering to obtain the water-based adhesive sample solution to be tested.
Further improvement, in the step one), the centrifugal separation temperature is 20-25 ℃, the rotating speed is 10000-15000 rpm, and the time is 5-10 min.
In a further improvement, the external standard method may be used to produce a standard curve in a conventional manner, but preferably the following process is used: 5 acetyl tributyl citrate standard working solutions (0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL and 1mg/mL) with the following concentrations were prepared, and standard curves were drawn with the peak areas as ordinate and the concentrations of the acetyl tributyl citrate standard working solutions as abscissa. A standard curve should be prepared for each test, a medium concentration standard solution should be added after each 20 times of sample measurement, and if the measured value is different from the original value by more than 5%, the standard curve should be drawn again.
In the invention, the content of acetyl tributyl citrate in a water-based adhesive sample is calculated according to the formula (1):
in the formula:
c-concentration of acetyl tributyl citrate in micrograms per milliliter (. mu.g/mL) in a sample of water-based gum derived from a standard curve;
C0-the concentration of tributyl acetylcitrate in micrograms per milliliter (. mu.g/mL) in the blank sample from the standard curve;
v-volume of extract in milliliters (mL);
k-dilution factor;
m-sample mass in grams (g).
The final measurement result is the average value of two parallel measurements, and the accuracy is 0.1 mg/kg.
The relative mean deviation of the parallel measurements should be less than 10%.
And if the concentration of the sample solution to be detected exceeds the concentration range of the standard working curve, changing the dilution multiple of the extraction liquid and then re-measuring.
The invention provides a simple, rapid and efficient method for determining acetyl tributyl citrate in water-based adhesive, which has the following advantages: 1) aiming at the characteristics of small dead volume and high sensitivity of a UPLC instrument pipeline, a sample pretreatment method is developed in a targeted manner, and C is added18Bonded silica gel is used as a dispersed solid phase extracting agent and diluted by a certain proportion of solvent, so that the interference of non-target substances in the matrix is greatly reduced; 2) according to the characteristics of the target compound, a new rapid analysis method is established by optimizing UPLC chromatographic conditions, and the determination time is less than 20 min.
Detection limit of the inventive method
The lowest concentration standard solution (0.01mg/mL) was selected and assayed in parallel 10 times, and the standard deviation was calculated with 3-fold standard deviation as the detection limit of the assay. The study showed that the limit of detection of the method was 0.005 mg/mL.
② recovery rate and repeatability of the inventive method
The recovery of the process was determined using standard addition methods. Weighing 0.5g of sample, adding the mixed standard solution with the content equivalent to the sample, extracting according to the pretreatment condition of the method, repeating for 6 times, and measuring the standard addition recovery rate and the repeatability, wherein the results are shown in table 1. The average recovery rate is 101.5%, and the RSD of a repeatability experiment is 4.8%, so that the requirement of quantitative analysis can be met.
TABLE 1 recovery and repeatability
Drawings
FIG. 1: example 1 of the invention a standard working solution chromatogram of 0.1mg/mL under chromatographic conditions;
FIG. 2: example 1 chromatogram of a sample of an aqueous gel under chromatographic conditions.
Detailed Description
The invention is further described below with reference to examples, but without limiting the invention.
Example 1:
1. instruments and reagents:
acetyl tributyl citrate (purity of more than 97%, Chiloei (Shanghai) chemical industry development Co., Ltd.), and chromatographic pure grade acetonitrile.
ACQUITY UPLC I-Class ultra high performance liquid chromatograph (waters), PDA detector (waters), Empower 3 chromatography workstation (waters); BP221S electronic balance (sensory 0.0001g, Sartorius, germany); VX-2500 type vortex oscillator (HENRY TROEMNER LLC, USA); Milli-Q ultra pure water machine (Millipore, USA); microporous organic filter membrane (0.22 μm, Shanghai' an spectral science apparatus Co., Ltd.).
2. Sample treatment:
0.5g of water-based adhesive sample is weighed into a conical flask, 10mL of acetonitrile solution is added, and 150mg of C is added18Dispersing the solid phase extractant, carrying out vortex oscillation for 5min, taking a small amount of extract liquor, carrying out centrifugal separation, and filtering with a 0.22 mu m organic filter membrane to obtain a sample solution to be detected.
3. Standard working solution:
standard working solutions of acetyl tributyl citrate (0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL, and 1mg/mL) were prepared at the following 5 concentrations.
4. And (3) sample determination:
the chromatographic conditions used for the determination were: a chromatographic column: atlantis T3
3mm × 100 mm; column temperature: 30 ℃; column flow rate: 0.6 mL/min; sample introduction amount: 2 mu L of the solution; detection wavelength: 212 nm. Mobile phase A: water; mobile phase B: acetonitrile; gradient elution procedure: linearly increasing the ratio of acetonitrile to water from 20:80 to 100% acetonitrile for 0-15 min; 15-20 min, 100% acetonitrile. Gradient elution for 20 min.
Respectively taking 0.5mL of standard working solutions with different concentrations, respectively carrying out UPLC-UV determination according to the sequence of the concentration from low to high, carrying out linear regression analysis on the measured UV peak area (y) and the mass concentration (x, mg/L) of the standard solution, and obtaining a standard curve equation of the target compound as follows: 752.93x +8365.3, coefficient of correlation R2Is 0.9995.
And (4) determining the extracted sample, determining the sample by retention time, determining the peak area value of the target object, substituting the peak area value into a standard curve equation, and solving the content of the acetyl tributyl citrate in the sample. (sample measurement chromatogram see FIG. 2)
TABLE 2 detection results of target in sample A
Example 2:
the specific detection procedure was as described in example 1, with another water-based gum sample B selected and the results are shown in table 3.
TABLE 3 detection results of target in sample B
Example 3:
the specific detection procedure was as described in example 1, with another water-based gum sample C selected and the results are shown in table 4.
TABLE 4 detection results of target in sample C
Claims (4)
1. A method for measuring the content of acetyl tributyl citrate in water-based adhesive is characterized by comprising the following steps:
step one), extracting acetyl tributyl citrate in a water-based adhesive sample by using acetonitrile, adding a C18 dispersed solid phase extracting agent, performing vortex oscillation and centrifugal separation, and filtering a supernatant by using a filter membrane to obtain a sample solution to be detected;
step two), preparing acetyl tributyl citrate standard curve solution;
step three), using an ultra-high performance liquid chromatograph and taking acetonitrile and water as mobile phases to carry out gradient elution analysis on the sample solution to be detected and the standard curve solution, and quantitatively measuring acetyl tributyl citrate by an external standard method; calculating the content of acetyl tributyl citrate in the raw water-based adhesive according to the measurement result;
the chromatographic conditions in the step three) are as follows: the chromatographic column is
Gradient elution procedure: linearly increasing the ratio of acetonitrile to water from 20:80 to 100% acetonitrile for 0-15 min; 15-20 min, 100% acetonitrile;
column temperature: 20-40 ℃; flow rate: 0.3-0.6 mL/min; sample introduction amount: 1-5 mu L; the detector is a diode array detector, and the detection wavelength is 212 nm;
weighing 0.5-1 g of water-based adhesive sample in the step one), placing the water-based adhesive sample in a conical flask, adding 5-20 mL of acetonitrile solution, carrying out vortex oscillation for 5min, taking a small amount of extract, carrying out centrifugal separation, and filtering with a 0.22 mu m organic filter membrane to obtain a water-based adhesive sample solution to be detected.
2. The method for determining the content of tributyl acetylcitrate in water-based adhesive of claim 1, wherein: the column temperature was 30 ℃, the flow rate was 0.6mL/min, and the sample size was 2. mu.L.
3. The method for determining the content of tributyl acetylcitrate in water-based adhesive of claim 1, wherein: the centrifugal separation temperature in the first step is 20-25 ℃, the rotating speed is 10000-15000 rpm, and the time is 5-10 min.
4. The method for determining the content of tributyl acetylcitrate in water-based adhesive of claim 1, wherein: the concentration of the standard curve solution of the acetyl tributyl citrate in the step two) is 0.01mg/mL, 0.05mg/mL, 0.1mg/mL, 0.5mg/mL and 1mg/mL in sequence.
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Citations (3)
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| CN103487542A (en) * | 2013-09-11 | 2014-01-01 | 湖南中烟工业有限责任公司 | Method for concurrently detecting 23 ester compounds in cigarette water-base adhesive |
| CN108152424A (en) * | 2018-02-08 | 2018-06-12 | 河南中烟工业有限责任公司 | The detection method of citric acid ester plasticizer content in a kind of cigarette paper wrapper |
| CN108426952A (en) * | 2018-02-08 | 2018-08-21 | 河南中烟工业有限责任公司 | The detection method of citric acid ester plasticizer content in a kind of essence spice for cigarette |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103487542A (en) * | 2013-09-11 | 2014-01-01 | 湖南中烟工业有限责任公司 | Method for concurrently detecting 23 ester compounds in cigarette water-base adhesive |
| CN108152424A (en) * | 2018-02-08 | 2018-06-12 | 河南中烟工业有限责任公司 | The detection method of citric acid ester plasticizer content in a kind of cigarette paper wrapper |
| CN108426952A (en) * | 2018-02-08 | 2018-08-21 | 河南中烟工业有限责任公司 | The detection method of citric acid ester plasticizer content in a kind of essence spice for cigarette |
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