CN116399976A - Method for measuring 2, 6-diisopropylaniline in biodegradable film - Google Patents
Method for measuring 2, 6-diisopropylaniline in biodegradable film Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
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- 239000002184 metal Substances 0.000 claims abstract description 5
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- 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
- G01N30/02—Column chromatography
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
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- G01N2030/042—Standards
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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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Abstract
The invention discloses a method for measuring 2, 6-diisopropylaniline in a biodegradable film, which comprises the following steps: s1, adding a biodegradable mulch fragment sample into a headspace bottle, adding a recovery rate correction internal standard solution, adding an acidic solution, placing in a constant-temperature metal bath for heating and extraction, cooling to room temperature, and filtering to obtain an extraction filtrate; s2, placing the extracted filtrate into a centrifuge tube, adding ultrapure water, adding a hydrophilic extractant, carrying out vortex mixing to obtain a homogeneous system, carrying out ice bath, adding an alkaline solution to adjust the pH, converting the hydrophilic extractant into a hydrophobic extractant in an alkaline environment, realizing two-phase separation, centrifuging, taking the upper liquid into another centrifuge tube, and centrifuging; s3, taking the upper organic solution in a microscale sample bottle, adding the internal standard solution corrected by the instrument, and carrying out GC-MS analysis by vortex mixing. The method has the advantages of rapidness, sensitivity, solvent saving and the like, has higher sensitivity compared with the traditional method, and can measure the total amount of 2,6-DIPA in the PBAT biodegradable film.
Description
Technical Field
The invention relates to a method for measuring 2, 6-diisopropylaniline in a biodegradable film, belonging to the technical field of biodegradable film additive measurement.
Background
The poly (butylene adipate/terephthalate) (PBAT) is an aliphatic-aromatic polyester which can be biodegraded, belongs to petrochemical-based biodegradable plastics, has good ductility and elongation at break, high toughness, high temperature resistance and excellent biodegradability, and is a fully biodegradable plastic. PBAT is a novel organic material which is considered to be the most promising to replace the traditional mulching film material to manufacture the biodegradable mulching film, is considered as one of sustainable materials generated by modern green materials, and is widely applied to the production of agricultural biodegradable mulching films. During processing, the PBAT biodegradable film can be added with different types of organic additives, such as anti-skid agents, lubricants, antioxidants, stabilizers, plasticizers, flame retardants, fillers, rubber aids, and the like. The ecotoxicological effects of plasticizer Phthalic Acid Esters (PAEs) in conventional plastics have been widely reported, and certain additives in PBAT have obvious toxic units and can be potential novel environmental pollutants, and can influence plant growth, development and soil microbial communities and functions. Studies have shown that evaluation of biodegradable materials must take into account the ecological impact of additives.
The 2,6-DIPA in the PBAT biodegradable film is mainly derived from degradation of the hydrolysis resistance additive N, N' -bis (2, 6-diisopropylphenyl) carbodiimide (BDICDI), which is first slowly degraded to the corresponding 2,6-DIPI as shown in fig. 1, and finally degraded to chemically stable and quantifiable 2,6-DIPA. Therefore, 2,6-DIPA and 2,6-DIPI are used as degradation byproducts, have important indication effects on evaluating the production process, the formulation quality and the performance change of the biodegradable film, and the 2,6-DIPA has structural similarity with aniline which is an environmental pollutant and can possibly have certain influence on the environment and the health of a human body, so that an analysis method of the 2,6-DIPA and the 2,6-DIPI is established to monitor the production process or evaluate the safety of related products.
However, due to the high reactivity of the isocyanato groups in 2,6-DIPI, the protonated solvent can convert the isocyanate to the corresponding by-product, resulting in an inaccurate quantification of the total amount of 2,6-DIPA (2, 6-DIPA and 2, 6-DIPI) in the PBAT biodegradable mulch, such as literature: cui, H, gao, W, lin, Y, et al development of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry for the determination of organic additives in biodegradable mulch films [ J ]. Microchemical Journal,2021,160;105722.
disclosure of Invention
Based on the above, the invention provides a method for measuring 2, 6-diisopropylaniline in a biodegradable film, which can accurately quantify the total amount of 2,6-DIPA (2, 6-DIPA and 2, 6-DIPI) in a PBAT biodegradable film so as to overcome the defects in the prior art.
The technical scheme of the invention is as follows: a method for determining 2, 6-diisopropylaniline in a biodegradable film comprising the steps of:
s1, adding a biodegradable mulch fragment sample into a headspace bottle, adding a recovery rate correction internal standard solution, adding an acidic solution, placing in a constant-temperature metal bath for heating, simultaneously extracting 2,6-DIPA and hydrolyzed 2,6-DIPI, cooling to room temperature, and filtering to obtain an extraction filtrate;
s2, placing the extracted filtrate into a centrifuge tube, adding ultrapure water, adding a hydrophilic extractant, carrying out vortex mixing to obtain a homogeneous system, carrying out ice bath, adding an alkaline solution to adjust the pH, converting the hydrophilic extractant into a hydrophobic extractant in an alkaline environment, realizing two-phase separation, centrifuging, and taking an upper liquid into another centrifuge tube;
s3, centrifuging the upper liquid obtained in the step S2 again, taking the upper organic solution in a microscale sample bottle, adding the internal standard solution corrected by the instrument, and carrying out GC-MS analysis by vortex mixing.
Preferably, in step S1, the recovery rate correction internal standard solution is 2, 6-diethylaniline, and the acidic solution is H 2 SO 4 The concentration is 3mol/L, the heating temperature is 90 ℃, and the time is 3h.
Preferably, in step S2, the hydrophilic extractant is n-dipropylamine, the amount is 100 μl, the alkaline solution is NaOH, the pH is adjusted to 14, and the extraction time is 1min.
Preferably, in step S3, the instrument-corrected internal standard solution is 2,4, 6-tri-tert-butylaniline.
Preferably, in step S3, the conditions for GC-MS analysis are: type of column: DB-5 capillary column, carrier gas: helium, the temperature programming condition is that the initial temperature is 40 ℃, and the temperature is kept for 1min; then at 10 ℃ for min -1 Heating to 230 ℃, and keeping for 1min; at 15 ℃ for min -1 Raising the temperature to 280 ℃, keeping the temperature of the sample inlet for 0 min: 280 ℃, sample injection amount: 1.0 mu L, split sample injection, split ratio: 20:1, constant flow rate: 1.0mL min -1 The total running time was 24.333min; ion source temperature: quadrupole temperature 230 ℃): 150 ℃; mass spectrometry transmission line temperature: solvent delay time at 280 ℃): the ionization mode is electron impact ionization of 70eV for 12min, and the Full Scan range is m/z=45-500 by adopting a Full Scan and selective ion Scan (SIM) mode.
Preferably, the biodegradable film is a poly (adipic acid)/butylene terephthalate degradable film.
The beneficial effects of the invention are as follows: the invention adopts the technology of combining heating, hydrolysis-extraction and switchable hydrophilic solvent homogeneous liquid-liquid phase microextraction with GC-MS chromatographic analysis to establish and verify the qualitative and quantitative methods of 2,6-DIPA in the biodegradable film. DPA is a switchable hydrophilic reagent, and the conversion from hydrophilic to hydrophobic of DPA is realized by adjusting the pH value, so that the extraction process is completed. The method has the advantages of rapidness, sensitivity, solvent saving and the like, has higher sensitivity compared with the traditional method, and can simultaneously determine the total amount of 2,6-DIPA in the PBAT biodegradable film. The invention can be used for monitoring the content of the additive 2,6-DIPA in the biodegradable mulch film, thereby carrying out production process monitoring or safety evaluation on related products and providing basic theoretical reference for the subsequent application of the biodegradable mulch film.
Compared with the prior art, the invention has the following advantages: 1. the qualitative and quantitative analysis method of the total amount of 2,6-DIPA (2, 6-DIPA and 2, 6-DIPI) in the PBAT biodegradable film is reported for the first time; 2. purifying and enriching 6-DIPA in the PBAT biodegradable film by adopting switchable hydrophilic solvent DPA homogeneous liquid-liquid microextraction; 3. the micro-extraction reduces the dosage of organic solvent, and has the advantages of quick extraction time, high efficiency, high enrichment coefficient and enrichment coefficient of 73.2-83.4; 4. the method has high sensitivity, accuracy and precision.
According to analysis, under the optimal test condition, the invention has good linear relation (the correlation coefficient r is more than or equal to 0.9986) on 2,6-DIPA within the range of 0.0144-7.200 mug/mL, the detection limit of the method is 0.0033 mug/g, the quantitative limit is 0.0103 mug/g, the recovery rate is 91.4-104.3%, and the precision range is 2.54-4.58%. The method has good linearity, detection limit, recovery rate and precision.
Drawings
FIG. 1 conversion of BDICDI to 2,6-DIPI and 2,6-DIPA in biodegradable mulch
FIG. 2 is a full-scan mass spectrum of target 2, 6-DIPA;
FIG. 3 gas chromatograph-mass spectrometer determination of standard curve for 2, 6-DIPA;
FIG. 4 hydrolysis rates of different hydrolysis solvents for 2,6-DIPI, BDICDI;
FIG. 5 different H 2 SO 4 Concentration versus hydrolysis rate of 2, 6-DIPI;
FIG. 6 hydrolysis rates of different temperatures versus 2, 6-DIPI;
FIG. 7 hydrolysis rates of different heating times versus 2, 6-DIPI;
FIG. 8 optimization of extracted organic reagent species for switchable hydrophilic solvent homogeneous liquid-liquid microextraction;
FIG. 9 optimization of extraction reagent volumes for switchable hydrophilic solvent homogeneous liquid-liquid microextraction;
FIG. 10 effect of different pH systems on switchable hydrophilic solvent homogeneous liquid-liquid microextraction;
FIG. 11 effect of different extraction times on switchable hydrophilic solvent homogeneous liquid-liquid microextraction.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
1. Test materials:
1. materials and reagents
PBAT biodegradable mulch, commercially available, is cut into pieces of about 2mm by 2 mm.
Acetone, methanol, 2,6-DIPI, BDICDI, 2,6-DIPA, triethylamine (TEA), sodium hydroxide (NaOH), hydrochloric acid (HCl), sulfuric acid (H) 2 SO 4 ) 2, 6-Diethylaniline (DEA), 2,4, 6-tri-tert-butylaniline (TBA), 2,4, 6-Trimethylaniline (TMA), N-dimethylbenzylamine (BDMA), di-N-propylamine (DPA), N-Dimethylcyclohexylamine (DMCHA), methanesulfonic acid (MSA) were all available from the company Ara Ding Shiji. Mother solutions of 10.800mg/mL and 10.300mg/mL are prepared from 2,6-DIPA and BDICDI standard solutions by using acetone, diluted and used, and solutions of 2.808 and 1.080mg/mL are respectively prepared from internal standard TBA and DEA standard solutions by using acetonitrile, and then the internal standard TBA and DEA standard solutions are stored at a low temperature of 5 ℃ for later use.
2. Apparatus and device
Agilent 7890A-5975C gas chromatograph-mass spectrometer (Agilent technologies Co., ltd.), constant temperature metal bath (Reheng instruments Co., hangzhou), vortex-1 Vortex meter (Migo instruments Co., hangzhou), HH-2 constant temperature water bath (Shanghai Mei Xiang instruments Co., ltd.), TDL-80-2B low speed centrifuge (Shanghai Anting scientific instruments Co., ltd.), milli-Q ultra pure water preparation device (Millipore Co., U.S.A.), ai Bende mini centrifuge (Ai Ben Germany), AL204-IC electronic balance (Metrer-Toli instruments Shanghai Co., ltd.).
2. Method for measuring 2, 6-diisopropylaniline in biodegradable film
The method for measuring 2, 6-diisopropylaniline in a biodegradable film comprises the following steps:
s1, accurately weighing 50mg of PBAT biodegradable mulch film sample in a 20mL headspace bottle, adding 10 mu L of 1.080mg/mLDEA internal standard solution, and adding 3mL of 3mol/LH 2 SO 4 Heating the solution in a constant temperature metal bath at 90 ℃ for 3 hours, simultaneously extracting 2,6-DIPA and hydrolyzed 2,6-DIPI, cooling to room temperature, passing through a 0.22 mu m organic filter membrane, and transferring the obtained extraction filtrate into a 10mL glass centrifuge tube for standby;
s2, taking 2mL of sample liquid into a 10mL centrifuge tube, adding 2mL of ultrapure water, adding 100 mu L of n-dipropylamine, and carrying out vortex mixing to observe a homogeneous system; ice bath for 2min, adding 12mol/LNaOH to adjust pH=14, fully vortex for 60s, realizing the separation of two phases, and completing the extraction process. Centrifugation was performed at 3000rpm for 5min, the upper layer (containing small amounts of impurities and water) was removed with a 100. Mu.L pipette into a 1.5mL centrifuge tube, centrifugation was performed at 3000rpm for 3min, a 50. Mu.L manual injection valve syringe was used, the upper organic solution was removed from the microscale flask (final upper organic solution was about 60. Mu.L), and 2. Mu.L of the internal standard solution was added with a 2.808mg/mLTBA instrument calibrated for vortex mixing for GC-MS analysis.
The conditions for GC-MS analysis were: type of column: DB-5 capillary column, carrier gas: helium, the temperature programming condition is that the initial temperature is 40 ℃, and the temperature is kept for 1min; then at 10 ℃ for min -1 Heating to 230 ℃, and keeping for 1min; at 15 ℃ for min -1 Raising the temperature to 280 ℃, keeping the temperature of the sample inlet for 0 min: 280 ℃, sample injection amount: 1.0 mu L, split sample injection, split ratio: 20:1, constant flow rate: 1.0mL min -1 The total running time was 24.333min; ion source temperature: quadrupole temperature 230 ℃): 150 ℃; mass spectrometry transmission line temperature: solvent delay time at 280 ℃): the ionization mode is electron impact ionization of 70eV for 12min, and the Full Scan range is m/z=45-500 by adopting a Full Scan and selective ion Scan (SIM) mode. The SIM quantitative ions for 2,6-DIPA, DEA and TBA are m/z 162, 134 and 226, respectively, and the qualitative ions are m/z 177,120, 149,119 and 261,230, respectively. FIG. 2 is a full-scan mass spectrum of the target 2,6-DIPA.
3. Method verification
1. Linear regression equation and detection limit
Under the implementation method conditions, 4 mu L, 8 mu L, 10 mu L, 50 mu L and 100 mu L of 2,6-DIPA with the concentration of 0.0108mg/mL are respectively taken, standard curves are respectively prepared from 1.080mg/mL, 10 mu L and 20 mu L of mother liquor, x is the concentration of 2,6-DIPA, y is the ratio of the peak area of 2,6-DIPA to the peak area of TBA, a standard curve between the peak area ratio (y) of the 2,6-DIPA and the peak area ratio (x) -2,6-DIPA is drawn, a linear equation is y= 0.2377x-0.0049, the linear equation has a good linear relation (correlation coefficient r is larger than or equal to 0.9986) in the range of 0.0144-7.200 mu g/mL, the detection limit is 0.0033 mu g/g by calculating the weight, dilution ratio, recovery rate and the like of the combined sample, and the quantitative limit is 0.0033 mu g/g. The standard curve at 8 concentrations of 2,6-DIPA is shown in FIG. 3 below, and from the results, the standard curve is wide in range and the linear correlation coefficient is good.
2. Accuracy and precision
30 portions of 50mg sample QC were weighed. 15 parts of low-concentration sample are added, wherein 10 parts of low-concentration sample are added, and 5 parts of blank sample are added, and 3 mu L of 1.080mg/mL of 2,6-DIPA standard solution and 6 mu L of blank sample are respectively added; 15 parts of the sample were added as high-concentration samples, 5 parts of the sample were used as blank samples, and 10 parts of the sample were added at a concentration of 10.800mg/mL of 2,6-DIPA standard solution 7. Mu.L and 14. Mu.L, and the sample was tested according to the optimized method, and after heating hydrolysis-extraction, micro-extraction was performed and analyzed by GC-MS. Recovery was calculated as the content of 2,6-DIPA minus the content of blank 2,6-DIPA divided by the content of added 2,6-DIPA and multiplied by 100% in the post-addition sample. The precision evaluation was performed with the measured deviations of the unlabeled and labeled samples, respectively. As shown in Table 1, the recovery rate of 2,6-DIPA is between 91.4% and 104.3%, the precision range is 2.54% to 4.58%, and the method has good accuracy, repeatability and stability, and is suitable for qualitative and quantitative analysis of 2,6-DIPA in PBAT biodegradable films.
TABLE 1 labeled recovery and precision of low/high content samples
4. Application case
10 samples of PBAT biodegradable films (PBAT-1, PBAT-2, PBAT-3, PBAT-4, PBAT-5, PBAT-6, PBAT-7, PBAT-8, PBAT-9, and PBAT-10) of different origins were collected, and the total amount of 2,6-DIPA in the samples was analyzed by the established method, and the results are shown in Table 2 below. 10 samples all contain 2,6-DIPA, and more than 85.1 mug/g, 2,6-DIPA mainly comes from degradation of hydrolytic inhibitor BDICDI, BDICDI is firstly converted into 2,6-DIPI and then degraded into 2,6-DIPA, which indicates that most of PBAT biodegradable mulch films are added with hydrolytic inhibitor BDICDI in the production process. Too high a 2,6-DIPA content (mg/g grade) also proves that the production process needs to be adjusted, and the degradation of BDICDI in the production process is reduced.
TABLE 2 analysis of 2,6-DIPA content in samples of 10 different sources of PBAT biodegradable films
The selection and heating of the internal standard reagent in the research process of the invention are detailed below, and the hydrolysis-extraction optimization and the SHS-HLLME extraction condition optimization are simultaneously carried out:
1. selection of internal standard reagents
The chromatographic analysis of the internal standard is to correct the recovery rate of the target and the sampling and response errors of the instrument, and the proper internal standard can lead the result to be more accurate, and the internal standard generally selects substances (like a system) with physical and chemical properties close to those of the target compound. Test DEA, TBA, TMA was selected as an internal standard for screening, pK of three substances a pK of 4.13, 3.30 and 5.38,2,6-DIPA, respectively a 4.25.TMA is too alkaline, tends to form tailing and produces a higher matrix effect at the sample inlet. pK of DEA a The value is similar to that of 2,6-DIPA, so DEA is added as an internal standard for recovery rate correction during hydrolysis-extraction of samples, TBA is weak in alkalinity and easy to lose during high-temperature heating, and TBA is added as an internal standard for instrument correction after sample enrichment and purification.
2. Simultaneous heating hydrolysis-extraction optimization
2.1 extraction of the hydrolysis solvent species
The PBAT biodegradable film contains free 2,6-DIPA and 2,6-DIPI, so that the test selects acid water solution to heat and extract and hydrolyze the 2,6-DIPA and 2,6-DIPI in the PBAT biodegradable film. Compared with other pretreatment methods (ultrasonic assisted extraction, soxhlet extraction, microwave assisted extraction, accelerated solvent extraction and heating extraction), the heating extraction method is simple and safe to operate, does not need expensive experimental equipment, and has the problems of large consumption of samples and organic solvents, large impurity interference, resource waste, environmental pollution, influence on measurement and analysis results and the like. Meanwhile, the acid aqueous solution can promote the hydrolysis of 2,6-DIPI by combining with heating extraction, so that the total amount of 2,6-DIPA is measured simultaneously.
Experiment at 3mol/L H 2 SO 4 Hydrolysis of 2,6-DIPI by 6mol/L HCl and 6mol/LMSA, evaluation of BDICDI hydrolysis rate, heating 100. Mu.L high concentration BDICDI standard solution (10.300 mg/mL) at 90deg.C for 3H hydrolysis, as shown in FIG. 4, 3 acids have no obvious difference in 2,6-DIPI hydrolysis efficiency, and H 2 SO 4 The hydrolysis efficiency of BDICDI is the lowest, the hydrolysis rate is only 0.65%, and the hydrolysis rates of HCl and MSA on BDICDI are all obviously higher than H 2 SO 4 Thus, select H 2 SO 4 And simultaneously extracting and hydrolyzing 2,6-DIPA and 2,6-DIPI in the PBAT biodegradable film. Under the conditions of HCl and MSA, BDICDI hydrolysis rate is higher, resulting in higher analysis results of 2,6-DIPA.
2.2H 2 SO 4 Concentration selection
Operating according to step S1, consider H 2 SO 4 The concentration (0.5 mol/L,1mol/L,2mol/L,3mol/L,4mol/L,6 mol/L) had a hydrolytic effect on 2,6-DIPI, as shown in the results of FIG. 5: with H 2 SO 4 Is increased in concentration of H 2 SO 4 The hydrolysis rate of 2,6-DIPI increases, and when the concentration is 3mol/L, the hydrolysis rate is 91%, the concentration continues to rise, and the hydrolysis rate of 2,6-DIPI is basically balanced. Therefore, 3mol/L H is selected 2 SO 4 Subsequent conditions are optimized to further increase the sulfuric acid concentration at risk of BDICDI hydrolysis.
2.3 heating temperature
With reference to the operation of step S1, the heating temperature was set to 50 ℃,70 ℃,90 ℃,110 ℃ respectively, and the optimum heating temperature was determined under the condition that other conditions were not changed. As the results in fig. 6 show: the hydrolysis rate of 2,6-DIPI is 39% when heated and hydrolyzed at 50 ℃, 64% when heated and hydrolyzed at 70 ℃, 92% when heated and hydrolyzed at 90 ℃, 93% when heated and hydrolyzed at 110 ℃, the increase of the heating temperature increases the hydrolysis rate, isocyanate in a sample is completely hydrolyzed when the temperature is 90 ℃, the hydrolysis rate is kept stable when the temperature is continuously increased, the optimal hydrolysis temperature is selected at 90 ℃, and the BDICDI hydrolysis risk exists when the heating temperature is increased.
2.4 heating time
To obtain the optimal hydrolysis-extraction time, the other conditions were kept unchanged, and the heating time was varied (1 h,2h,3h,6h,12 h) by operating according to step S1, as the results in fig. 7 show: h in the range of 1H to 3H along with the extension of heating time 2 SO 4 The hydrolysis rate product of the mulch film sample is gradually increased, the hydrolysis rate is 95% in 3 hours, and the mulch film sample is basically stable and unchanged after 3 hours, which shows that the hydrolysis rate is higher in 3 hours and the hydrolysis rate is kept unchanged, and isocyanate is basically completely hydrolyzed and extracted. 3h was chosen as the optimal hydrolysis-extraction time.
3. SHS-HLLME extraction condition optimization
Sample purification is an indispensable step for analyzing and detecting a target compound. Typical purification methods include dispersion-liquid microextraction (DLLME), solid Phase Extraction (SPE), solid Phase Microextraction (SPME), switchable hydrophilic solvent homogeneous liquid-liquid microextraction (SHS-HLLME), and other extraction techniques. SHS-HLLME is a green and efficient extraction technique proposed by jessep et al in 2010, which uses a Switchable Hydrophilic Solvent (SHS) as the extraction phase. SHS is a solvent that can be reversibly switched between two forms, homogeneous miscible and two-phase mixtures, and mainly includes Dipropylamine (DPA), triethylamine (TEA), N-diethyl butylamine (DEBA), N-dimethyl cyclohexylamine (DMCHA), and the like. The hydrophilic and hydrophobic transformation of the switchable hydrophilic solvent can be completed by adjusting the pH value, so that emulsion of countless small organic liquid drops is formed in a short time, the maximum contact area of two phases is realized, and the extraction efficiency is improved. Compared with the other three pretreatment technologies, the SHS-HLLME has the advantages of being quick in extraction time, high in extraction efficiency, high in enrichment coefficient and the like. In addition, the SHS-HLLME reduces the dosage of organic solvents, has low cost and small pollution to the environment, is a green and efficient extraction technology, and therefore, the SHS-HLLME is selected as the purification method of the invention.
In the process of SHS-HLLME microextraction, the factors such as the type and the amount of SHS, the adjustment of the pH value of phase separation and the extraction time of the phase separation of the SHS are mainly used for influencing the extraction efficiency, and in order to obtain the optimal microextraction efficiency of 2,6-DIPA, the peak area (R) of the extracted 2,6-DIPA is multiplied by the volume (V) of the final hydrophilic reagent org ) Ratio to TBA peak area (R IS ) The extraction efficiency was evaluated.
3.1SHS species
Hydrophilic agents need to meet the following two conditions to possess switchable properties: first, n-octanol/water partition coefficient (log K ow ) Must be between 1.2 and 2.5, with a low logarithmic K ow Is too hydrophilic and forms a single phase mixture with water in neutral form, with a high logarithmic K ow Is too hydrophobic, forming a two-phase mixture with water; second, the conjugate acid strength coefficient pK a Approaching 9.5 or higher, if the reagent is not sufficiently basic, its reaction with carbonated water is insufficient to switch from a two-phase mixture to a single-phase mixture. Based on the data, log K of n-Dipropylamine (DPA) is displayed ow ＝1.64，pK a =11.05; log K of Triethylamine (TEA) ow ＝1.47，pK a =10.68; log K of N, N-Dimethylcyclohexylamine (DMCHA) ow ＝2.04，pK a =10.48; log K of N, N-dimethylbenzylamine (BDMA) ow ＝1.86，pK a =9.03, the 4 reagents selected all had switchable properties [20 ]]。
According to the single variable investigation mode, under the condition that other conditions are fixed, 200 mu LDPA, TEA, DMCHA, BDMA homogeneous hydrophilic reagents are respectively added into the test tube, the switchable hydrophilic solvent homogeneous liquid-liquid microextraction is carried out according to the operation of the step S2, the result shows that 4 solvents can realize phase separation, and the result of fig. 8 shows that: the minimum extraction volume of TEA and lower efficiency indicate that the water solubility is larger, BDMA shows more interference peaks, the extraction effects of DPA and DMCHA are compared, the extraction efficiency of DPA and DMCHA is similar, the extraction efficiency error of DMCHA is larger, and DPA is selected as the optimal hydrophilic extractant.
3.2 DPA usage of SHS
In the SHS-HLLME extraction process, the use amount of homogeneous DPA directly influences the extraction efficiency and the enrichment factor. In order to obtain the optimal amounts of homogeneous DPA, the amounts of 50, 80, 100, 150, 200, 250. Mu.L were examined, respectively, by following the procedure of step S2, under otherwise unchanged conditions, and the test results are shown in FIG. 9. 50 μldpa fails to form an effective organic layer. 80-250 mu L of the extract increases along with the increase of the using amount of the homogeneous DPA; when the dosage reaches 100 mu L, the extraction efficiency is basically kept unchanged, and the enrichment multiple reaches the maximum, so that the optimal dosage of the homogeneous DPA is 100 mu L.
3.3 pH value of phase separation of SHS homogeneous phase
Literature reports that acid solutions can be used instead of dry ice CO 2 In the form of (a) to obtain a homogeneous hydrophilic reagent. The sample hydrolysis-extraction solution in this experiment was H 2 SO 4 Solution, 3M H 2 SO 4 The solution was sufficient to allow DPA to form a homogeneous solution of numerous droplets, with no adjustment of the homogeneous pH to reduce the number of test steps. After the homogeneous phase is formed, the pH value needs to be adjusted to enable the hydrophilic DPA to be converted into the hydrophobic DPA in an alkaline environment, so that two-phase separation is realized, and the extraction process is completed. The pH of the system directly affects the extraction efficiency. The pH of the whole system was adjusted using 12mol/LNaOH and was adjusted to 8, 10, 12, 14 after DPA addition, respectively. The results in fig. 10 show that: at a pH of 8, the separation of the organic phase does not occur. With the increase of the pH value, the volume of the extracted DPA is gradually increased; at pH 14, the extraction efficiency of 2,6-DIPA was maximized, and therefore, optimal phase separation conditions were obtained at ph=14.
3.4 extraction time
In the SHS-HLLME extraction process, the extraction time is defined as the time from the addition of NaOH to separate the two phases before transfer to the centrifuge for centrifugation. Under the condition of the other conditions, the extraction time (0.5 mm, 1min,2min,3min,4min,5 min) pairs of the extraction times are respectively examinedEffect of efficiency. As the results in FIG. 11 show, the SHS-HLLME extraction process is completed in a short period of time, maintaining a substantially equilibrium state at various times of extraction. This is due to the fact that the homogeneous DPA is miscible with the sample, H in the sample solution when NaOH is added 2 SO 4 The aqueous phase is rapidly neutralized, the hydrophilic DPA is rapidly converted into the hydrophobic DPA, innumerable organic droplets are formed, and the whole sample solution is changed into an emulsion, so that the full contact between the organic phase and the aqueous phase is realized, and the 2,6-DIPA can transfer the sample into the DPA in a short time, thereby rapidly completing the extraction. The optimal extraction time was chosen to be 1min.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A method for determining 2, 6-diisopropylaniline in a biodegradable film comprising the steps of:
s1, adding a biodegradable mulch fragment sample into a headspace bottle, adding a recovery rate correction internal standard solution, adding an acidic solution, placing in a constant-temperature metal bath for heating, simultaneously extracting 2,6-DIPA and hydrolyzed 2,6-DIPI, cooling to room temperature, and filtering to obtain an extraction filtrate;
s2, placing the extracted filtrate into a centrifuge tube, adding ultrapure water, adding a hydrophilic extractant, carrying out vortex mixing to obtain a homogeneous system, carrying out ice bath, adding an alkaline solution to adjust the pH, converting the hydrophilic extractant into a hydrophobic extractant in an alkaline environment, realizing two-phase separation, centrifuging, and taking an upper liquid into another centrifuge tube;
s3, centrifuging the upper liquid obtained in the step S2 again, taking the upper organic solution in a microscale sample bottle, adding the internal standard solution corrected by the instrument, and carrying out GC-MS analysis by vortex mixing.
2. The method for measuring 2, 6-diisopropylaniline in biodegradable film according to claim 1, wherein in step S1, the recovery rate correction internal standard solution is 2, 6-diethylaniline, and the acidic solution is H 2 SO 4 The concentration is 3mol/L, the heating temperature is 90 ℃, and the time is 3h.
3. The method for measuring 2, 6-diisopropylaniline in a biodegradable film according to claim 1, wherein in step S2, the hydrophilic extractant is n-dipropylamine in an amount of 100 μl, the alkaline solution is NaOH, the pH is adjusted to 14, and the extraction time is 1min.
4. The method for measuring 2, 6-diisopropylaniline in a biodegradable film according to claim 1, wherein in step S3, the internal standard solution for instrument correction is 2,4, 6-tri-tert-butylaniline.
5. The method for determining 2, 6-diisopropylaniline in a biodegradable film according to claim 1, wherein in step S3, the GC-MS analysis conditions are: type of column: DB-5 capillary column, carrier gas: helium, the temperature programming condition is that the initial temperature is 40 ℃, and the temperature is kept for 1min; then at 10 ℃ for min -1 Heating to 230 ℃, and keeping for 1min; at 15 ℃ for min -1 Raising the temperature to 280 ℃, keeping the temperature of the sample inlet for 0 min: 280 ℃, sample injection amount: 1.0 mu L, split sample injection, split ratio: 20:1, constant flow rate: 1.0mLmin -1 The total running time was 24.333min; ion source temperature: quadrupole temperature 230 ℃): 150 ℃; mass spectrometry transmission line temperature: solvent delay time at 280 ℃): the ionization mode is electron impact ionization of 70eV for 12min, and the FullScan range from m/z=45 to 500 by adopting a full scan and selective ion Scan (SIM) mode.
6. The method of determining 2, 6-diisopropylaniline in a biodegradable film according to claim 1 wherein the biodegradable film is a poly (adipic acid)/butylene terephthalate degradable film.
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