CN112255356B - Qualitative and quantitative analysis method for bisphenol antioxidant in plastic - Google Patents
Qualitative and quantitative analysis method for bisphenol antioxidant in plastic Download PDFInfo
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Abstract
The invention discloses a qualitative and quantitative analysis method of bisphenol antioxidants in plastics, which comprises the steps of dissolving the plastics in tetrahydrofuran, adding an adsorbent to enrich bisphenol antioxidants (such as bisphenol antioxidants of 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2' -methylene-bis (4, 6-di-tert-butylphenol) and the like) in a water phase, desorbing the bisphenol antioxidants by using methanol, and filtering the mixture for high performance liquid chromatography analysis. The advantages of the invention are mainly reflected in that: (1) the pretreatment process of the sample is simple, and only scissors are needed to cut the sample; (2) by preparing the specific adsorbent, an efficient enrichment method is developed, the method is rapid and convenient, the substrate interference is small, and batch test is easy to realize; (3) the enrichment process uses less organic solvent, and the desorption process can be completed only by 0.5 h; (4) can realize qualitative and quantitative analysis of the bisphenol antioxidants at normal temperature.
Description
Technical Field
The invention relates to a method for enriching and detecting an additive in a high molecular polymer, in particular to a qualitative and quantitative analysis method for a bisphenol antioxidant in plastic.
Background
Plastics are high molecular compounds polymerized by polycondensation or polyaddition, are light in weight, stable in chemical properties, corrosion-resistant, easy to mold, and low in processing cost, and are widely applied to the aspects of electronics, electric appliances, automobiles, buildings, packaging, medical instruments, daily commodities, food and the like.
However, most plastics have poor temperature resistance and are easy to age, for example, polycarbonate resin (PC) is a biodegradable material, and has excellent comprehensive performance, outstanding impact resistance, transparency and dimensional stability, wide application temperature range, and excellent mechanical strength and electrical insulation, and is one of five general engineering plastics, and the yield and consumption of the engineering plastics are the first. Because of good biocompatibility, the material can be applied to the fields of surgical suture, bone fixing material, drug controlled release and the like. However, the carbonate bonds existing in the PC molecular chain are sensitive to water and heat, and are degraded into neutral diol/phenol and carbon dioxide through hydrolysis, alcoholysis and other processes under high-temperature aerobic and humid environments, so that the performance of the polycarbonate is seriously influenced. At present, PC products on the market need to be added with different antioxidant systems to improve the processing stability.
Bisphenol antioxidants, such as 2,2 '-methylenebis (4-methyl-6-tert-butylphenol) and 2, 2' -methylenebis (4, 6-di-tert-butylphenol), are versatile strongly hindered phenolic antioxidants with high melting point, low volatility, good protection against heat and oxygen induced aging and light radiation induced surface cracking aging, deactivation of valence-altering metal ions, and low color rendering, and are therefore widely used in a variety of plastics, rubbers, latexes, and petroleum products. The addition amount is usually 0.1-1.0%, which can endow the finished product with excellent oxidation resistance and prolong the service life of the finished product.
However, it is shown that the LD50 of 2, 2' -methylenebis (4-methyl-6-tert-butylphenol) is 6.5g/kg, and when the amount is excessively added, the migration and dissolution process thereof poses a threat to the health of human bodies and the safety of water resources. At present, food packaging materials at home and abroad make relevant regulations on the use amount of 2, 2' -methylenebis (4-methyl-6-tert-butylphenol). The national standard GB/T9685-2016 food safety food contact material and product additive use standard is established in China, and the limit requirements of 2, 2' -methylene bis (4-methyl-6-tert-butylphenol) are specified in detail: polyethylene (PE) and polypropylene (PP) are less than or equal to 0.1 percent, Polystyrene (PS) is less than or equal to 0.4 percent, acrylonitrile-styrene copolymer (AS) is less than or equal to 0.6 percent, acrylonitrile-butadiene-styrene copolymer (ABS) is less than or equal to 2 percent, and Polyformaldehyde (POM) is less than or equal to 0.5 percent. The U.S. food and drug administration specifies that the maximum amount of polyolefin used is the same as that used in china, but emphasizes that the article must not contact a surface greasy food. The rules in japan are: PE and PP are less than or equal to 0.1 percent, PS is less than or equal to 0.4 percent, AS is less than or equal to 0.6 percent, ABS is less than or equal to 2 percent, and polyvinyl chloride (PVC) is less than or equal to 2 percent.
At present, no related standard detection method exists at home and abroad to standardize the qualitative and quantitative analysis of the bisphenol antioxidants in the plastic products, and particularly, no provision is made for biodegradable PC products with increasing use amount. For human health and water resource safety, it is urgently needed to establish a related detection method. The bisphenol antioxidant is added in a low amount in the PC product, and can be effectively separated from the matrix material by using a large amount of organic solvent, so that the interference of a substrate substance is prevented. However, the currently established testing method for antioxidants in plastic products is basically to grind the products at low temperature and then extract the products with organic solvents, which is complicated in process and needs to consume more organic solvents. Therefore, the establishment of a rapid, efficient, convenient and fast qualitative and quantitative analysis method for organic solvents becomes a trend.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a rapid, efficient, convenient and fast qualitative and quantitative analysis method for hindered phenol bisphenol antioxidants in plastics with a small usage amount of organic solvents, so as to solve the problems of complex pretreatment and serious substrate interference in the prior art, and provide an analysis thought for quantitative detection of additives in high polymer materials.
In order to achieve the purpose, the technical scheme adopted by the invention is a qualitative and quantitative analysis method of bisphenol antioxidants in plastics, which is operated according to the following steps,
a. taking a plastic resin sample, shearing the plastic resin sample by using a pair of scissors, transferring the plastic resin sample into a 100mL conical flask, and adding tetrahydrofuran to dissolve the sample;
b. after the sample in the conical flask is completely dissolved, adding ultrapure water and an adsorbent, adjusting the pH to 9, stirring and extracting at normal temperature for 4 hours, and filtering;
c. transferring the filtered solid into a 50mL conical flask, adding a methanol solution, stirring and desorbing for 0.5h, filtering after desorption, flushing the adsorbent with a small amount of methanol, combining the adsorbent into desorption solution, accurately measuring the volume V of the total solution, taking a proper amount of desorption solution, filtering by using a 0.22 mu m membrane, and directly performing qualitative and quantitative analysis by using a high performance liquid chromatography;
d. repeating the steps a to C by taking the hollow conical bottle as a reference, manufacturing a blank, and marking the concentration as C0;
e. finally, quantification was performed using an external standard method.
Preferably, the preparation method of the adsorbent in the step b is as follows:
firstly, respectively transferring 4-vinylpyridine and ethylene glycol dimethacrylate into a n-propanol/1, 4-dibutanol (3:2, V/V) mixed solution, uniformly mixing, adding azobisisobutyronitrile, ultrasonically dispersing for 20min, introducing nitrogen to remove oxygen for 10min, pouring into a reactor, and carrying out closed reaction for 12h at 70 ℃;
step two, after the polymerization reaction is finished, taking out the solid, grinding and crushing the solid, and sieving the solid by a 100-mesh sieve;
and thirdly, soaking the sieved powder in methanol for activation for 12 hours, taking out the powder from the methanol when in use, filtering and drying the powder for enrichment analysis of a subsequent substance to be detected.
Preferably, in the step c, high performance liquid chromatography is used for qualitative and quantitative analysis, and the test conditions are as follows: a chromatographic column: c18(250 mm. times.4.6 mm, 5 μm); mobile phase: water (A) -acetonitrile (B) (gradient elution procedure: 0-10min, 30% B; 10-15min, 70% B; 15-20min, 30% B); flow rate: 0.7 mL/min; column temperature: 30 ℃; sample introduction volume: 20 mu L of the solution; detection wavelength: 275nm, detector: and the retention time of the diode array is used as a qualitative basis, and the peak area response is used as a quantitative basis.
Preferably, the plastic resin in step a is polycarbonate, polypropylene or a plastic resin that can be dissolved by the above-mentioned tetrahydrofuran.
Preferably, the hindered phenol type bisphenol antioxidant is an antioxidant having a bisphenol hydroxyl group, and includes 2,2 '-methylenebis (4-methyl-6-tert-butylphenol) and 2, 2' -methylenebis (4, 6-di-tert-butylphenol).
Preferably, after the adsorbent is enriched in the step b, the adsorbent is directly filtered and dried without a methanol desorption process, and then the surface morphology characteristics of the adsorbent are tested by using a scanning electron microscope, and the functional groups contained in the adsorbent are tested by using Fourier transform infrared.
Preferably, after the preparation of the adsorbent is finished, the surface morphology characteristics of the adsorbent are tested by using a scanning electron microscope, and the functional groups contained in the adsorbent are tested by using Fourier transform infrared.
Compared with the prior art, the invention has the following technical effects.
(1) The pretreatment process of the sample is simple, and only scissors are needed to cut the sample.
(2) By preparing the specific adsorbent, an efficient enrichment method is developed, the method is rapid and convenient, the substrate interference is small, and batch test is easy to realize.
(3) The enrichment process uses a small amount of organic solvent, the desorption process can be completed only by 0.5 hour, the operation method is convenient and quick, and the batch treatment is easy to realize.
(4) Can realize qualitative and quantitative analysis of the bisphenol antioxidants at normal temperature.
Drawings
FIG. 1 is a scanning electron micrograph and an infrared spectrum of 2, 2' -methylenebis (4, 6-di-tert-butylphenol) before and after adsorption by the adsorbent of the present invention.
FIG. 2 is an infrared spectrum of 2, 2' -methylenebis (4, 6-di-tert-butylphenol) in the stripping liquid of the present invention.
FIG. 3 is a liquid chromatogram of 2, 2' -methylenebis (4, 6-di-tert-butylphenol) according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The present invention will be described in more detail with reference to polycarbonate resins as examples.
Preparation of the adsorbent:
1. 1.0mL of 4-vinylpyridine and 8mL of ethylene glycol dimethacrylate were respectively transferred and dissolved in 20mL of n-propanol/1, 4-dibutanol (3:2, V/V) mixed solution, and after uniform mixing, 10mg of azobisisobutyronitrile was added. After ultrasonic dispersion for 20min, introducing nitrogen to remove oxygen for 10min, pouring into a reactor, and carrying out closed reaction for 12h at 70 ℃.
2. After the polymerization reaction, the solid is taken out, ground and crushed, and sieved by a 100-mesh sieve.
3. And soaking the sieved powder in methanol for activation for 12 h. Taken out of methanol before use, filtered and dried. And the method is used for enrichment analysis of subsequent substances to be detected.
Secondly, sample pretreatment
Taking the polycarbonate resin, shearing the polycarbonate resin by using scissors, and weighing 0.3-0.5g of the sheared sample into a 100mL conical flask.
Thirdly, enriching the substance to be detected
5mL of tetrahydrofuran was added to the flask to dissolve the sample. After the sample is completely dissolved, 100mL of ultrapure water and 100mg of adsorbent are added, the pH is adjusted to 9, and the mixture is stirred, extracted for 4 hours and then filtered. The filtered solid was transferred to a 50mL Erlenmeyer flask, 10mL methanol solution was added, and desorption was carried out with stirring for 0.5 h. After desorption, filtration is carried out, and the adsorbent is washed by a small amount of methanol and then is combined into desorption liquid. After the volume V of the total solution is accurately determined, a proper amount of desorption solution is taken, and is directly subjected to chromatographic analysis after being filtered by a 0.22 mu m membrane.
After adsorbing with an adsorbent, ultrapure water or the like in the above procedure with reference to an empty conical flask, the methanol solution was desorbed to prepare a blank, the concentration of which was designated as C0.
Fourthly, analyzing conditions of liquid chromatography:
a chromatographic column: c18(250 mm. times.4.6 mm, 5 μm)
Mobile phase: water (A) -acetonitrile (B)
Gradient elution procedure: 0-10min, 30% B; 10-15min, 70% B; 15-20min, 30% B
Flow rate: 0.7mL/min
Column temperature: 30 deg.C
Sample introduction volume: 20 μ L
Detection wavelength: 275nm
A detector: an array of diodes.
Fifthly, external standard method quantification:
7 standard use solutions with different concentrations are prepared from the standard stock solution, the concentrations are respectively 1 mu g/mL, 5 mu g/mL, 10 mu g/mL, 20 mu g/mL, 50 mu g/mL, 100 mu g/mL and 200 mu g/mL, the concentration is used as an abscissa, the chromatographic peak area is used as an ordinate, and a standard working curve y is drawn as ax + b.
And (4) correspondingly taking the peak area obtained after the chromatographic analysis of the sample to be detected as an A sample, substituting the A sample into the working curve, and calculating to obtain the concentration C of the desorption solution.
Calculating the content (mg/kg) of bisphenol in the plastic according to the formula (1):
in the formula:
c: the concentration of the desorption solution is mu g/mL;
c0: the concentration of a blank desorption solution is mu g/mL;
v: the total volume of desorption solution is mL;
m: the mass of the resin to be detected, g;
w: bisphenol antioxidant content, mg/kg.
The test method takes the average value of three parallel measurements as a final measurement result, and the relative standard deviation of the parallel measurement result is less than 10%.
Sixthly, the limit of detection (LODs is 3Sb/m) and the limit of quantification (LOQs is 10Sb/m) of the method
The blank solution was run in parallel 7 times and the standard deviation Sb was calculated as the slope of the standard working curve m. The detection limit and the quantification limit were calculated to be 0.19. mu.g/mL and 0.63. mu.g/mL, respectively.
Seventh, the recovery and repetition rate of the process
The recovery of spiked samples was determined by adding two different spiked amounts (10. mu.g/mL and 100. mu.g/mL) to the actual samples. Each set of samples was tested in 5 replicates and the repetition rate was calculated and only 2, 2' -methylenebis (4, 6-di-tert-butylphenol) was detected in the actual samples.
TABLE 1 blank and spiked recovery for two samples
Table 1 Results of determination and recoveries of real samples spiked with 2,2'-Methylenebis(6-tert-butyl-4-methylphenol)
FIG. 1 shows the surface conditions of the prepared adsorbent before and after enrichment observed by electron microscopy, and infrared analysis is performed at the same time. FIG. 2 is an infrared spectrum of 2, 2' -methylenebis (4, 6-di-tert-butylphenol); FIG. 3 is a liquid chromatogram of 2, 2' -methylenebis (4, 6-di-tert-butylphenol).
As can be seen from a scanning electron microscope image, the aperture is large before adsorption, so that the adsorption and desorption processes are facilitated; after the adsorption process is finished, polymer particles are compact, and the pore diameter is small; indicating that the test object occupies these spaces. As can be seen from the infrared spectrogram, absorption peaks of 1454.7cm-1, 1602.6cm-1 and 2980.3cm-1 are respectively found in the figures before and after the adsorption of the template molecule, and are respectively classified into a stretching vibration absorption peak of C ═ C in the pyridine ring, a stretching vibration absorption peak of C ═ N in the pyridine ring and an absorption peak of-CH. When the substance to be tested is adsorbed, a vibration absorption peak (1516.9cm-1) of the benzene ring skeleton appears, which indicates that the substance to be tested is adsorbed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principles of the present invention are intended to be included therein.
Claims (3)
1. A qualitative and quantitative analysis method for bisphenol antioxidants in plastics is characterized by comprising the following steps: the bisphenol antioxidant is an antioxidant with bisphenol hydroxyl, 2, 2' -methylene bis (4, 6-di-tert-butylphenol), and is operated according to the following steps,
a. taking a plastic resin sample, shearing the plastic resin sample by using scissors, transferring the plastic resin sample into a 100mL conical flask, and adding tetrahydrofuran to dissolve the sample, wherein the plastic resin is polycarbonate, polypropylene or plastic resin which can be dissolved by the tetrahydrofuran;
b. after the sample in the conical flask is completely dissolved, adding ultrapure water and an adsorbent, adjusting the pH to 9, stirring and extracting at normal temperature for 4 hours, and filtering;
c. transferring the filtered solid into a 50mL conical flask, adding a methanol solution, stirring and desorbing for 0.5h, filtering after desorption, flushing the adsorbent with a small amount of methanol, combining the adsorbent into desorption solution, accurately measuring the volume V of the total solution, taking a proper amount of desorption solution, filtering by using a 0.22 mu m membrane, and directly performing qualitative and quantitative analysis by using a high performance liquid chromatography;
d. repeating the steps a to C by taking the hollow conical bottle as a reference, and preparing a blank with the concentration of C0;
e. finally, quantifying by using an external standard method;
the preparation method of the adsorbent in the step b comprises the following steps:
firstly, respectively transferring 4-vinylpyridine and ethylene glycol dimethacrylate into a n-propanol/1, 4-dibutanol mixed solution with the V/V of 3:2, uniformly mixing, adding azodiisobutyronitrile, ultrasonically dispersing for 20min, introducing nitrogen to remove oxygen for 10min, pouring into a reactor, and carrying out closed reaction for 12h at 70 ℃;
step two, after the polymerization reaction is finished, taking out the solid, grinding and crushing the solid, and sieving the solid by a 100-mesh sieve;
thirdly, soaking the sieved powder in methanol for activation for 12 hours, taking out the powder from the methanol when in use, filtering and drying the powder for enrichment analysis of a subsequent substance to be detected;
in the step c, high performance liquid chromatography is used for qualitative and quantitative analysis, and the test conditions are as follows: a chromatographic column: c18, 250mm × 4.6mm, 5 μm; mobile phase: water a-acetonitrile B, gradient elution procedure: 0-10min, 30% B; 10-15min, 70% B; 15-20min, 30% B; flow rate: 0.7 mL/min; column temperature: 30 ℃; sample introduction volume: 20 mu L of the solution; detection wavelength: 275nm, detector: and the retention time of the diode array is used as a qualitative basis, and the peak area response is used as a quantitative basis.
2. The method for qualitatively and quantitatively analyzing the bisphenol antioxidants in the plastics as claimed in claim 1, wherein: and c, directly filtering and drying the adsorbent without a methanol desorption process after the adsorbent is enriched in the step b, testing the surface morphology characteristics of the adsorbent by using a scanning electron microscope, and testing the functional groups contained in the adsorbent by using Fourier transform infrared.
3. The method for qualitatively and quantitatively analyzing the bisphenol antioxidants in the plastics as claimed in claim 1, wherein: after the preparation of the adsorbent is finished, the surface morphology characteristics of the adsorbent are tested by using a scanning electron microscope, and the functional groups contained in the adsorbent are tested by using Fourier transform infrared.
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