CN115060807B - Analysis method of stabilizer - Google Patents
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- CN115060807B CN115060807B CN202210048342.5A CN202210048342A CN115060807B CN 115060807 B CN115060807 B CN 115060807B CN 202210048342 A CN202210048342 A CN 202210048342A CN 115060807 B CN115060807 B CN 115060807B
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 59
- 238000004458 analytical method Methods 0.000 title abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 238000010828 elution Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 9
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 4
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical group CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims abstract description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 40
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 35
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 34
- 229950000688 phenothiazine Drugs 0.000 claims description 34
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 29
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 45
- 239000013558 reference substance Substances 0.000 description 36
- 239000012490 blank solution Substances 0.000 description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 239000012088 reference solution Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 5
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 4
- 238000012417 linear regression Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006084 composite stabilizer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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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- G01N30/06—Preparation
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- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/30—Control of physical parameters of the fluid carrier of temperature
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- G01N30/28—Control of physical parameters of the fluid carrier
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Abstract
The invention discloses an analysis method of a stabilizer, which comprises the following steps: detecting the sample by high performance liquid chromatography under the following chromatographic conditions: the stationary phase is octadecylsilane chemically bonded chromatographic column, and the mobile phase A is acidic aqueous solution; the mobile phase B is methanol, the mobile phase C is acetonitrile, and gradient elution is carried out. The invention can effectively separate 7 stabilizers, has short detection time and is convenient to operate; the invention has high sensitivity and good reproducibility.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to an analysis method of a stabilizer.
Background
Acrylic acid (ester) is an important petrochemical product and raw material, and is widely applied to the fields of high polymer materials, organic synthesis and the like. The acrylic acid (ester) molecular structure is easy to generate polymerization reaction due to unstable carbon-carbon double bond functional groups, and certain difficulties are brought to production, transportation and storage. Therefore, a certain amount of stabilizer is often added to the acrylic reagent to stabilize it. According to investigation, 7 stabilizers are commonly used in acrylic acid (ester) reagents on the market at present, namely Hydroquinone (HQ), p-hydroxyanisole (MEHQ), p-tert-butylcatechol (TBC), phenothiazine (PTA), 2, 4-dimethyl-6-tert-butylphenol (TBX), 2, 6-di-tert-butyl-p-methylphenol (BHT) and 2,2' -methylenebis (6-tert-butyl-4-Methylphenol) (MBP). The stabilizer is added in 2 modes, one mode is to add a single stabilizer into a certain acrylic acid (ester), and the other mode is to add 2 or 3 composite stabilizers of the 7 stabilizers into a certain acrylic acid (ester), so that the stabilizing effect is improved. Although the use of stabilizers can enhance the effectiveness of acrylic acid (ester) stabilization, the addition of stabilizers can also have an impact on the purity and conversion of the product downstream of the acrylic acid (ester). Therefore, when an acrylic reagent is used, it is necessary to perform analytical detection of the stabilizer therein.
Currently, there are reports on a method of analyzing a stabilizer in acrylic acid (ester) mainly including spectrophotometry, gas chromatography and liquid chromatography. The spectrophotometry is complicated to operate, time-consuming and labor-consuming, and the sensitivity of the instrument is low, so that the application range of the spectrophotometry is limited. The gas chromatography has the advantages of small sample injection amount, high analysis speed, high sensitivity and accuracy, and has higher use frequency in the field of petrochemical analysis, but is not suitable for the analysis of the stabilizer with higher boiling point and poor thermal stability. High performance liquid chromatography can solve the problems of high boiling point and poor thermal stability of stabilizers, however, previous studies have focused on analysis of one or both stabilizers in certain acrylates, and the application range has been limited.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides an analysis method of the stabilizer, which can effectively separate 7 stabilizers, has the separation degree of more than 1.5, has short detection time, can rapidly detect, has simple treatment of the test sample and is convenient to operate; the invention has high sensitivity and good reproducibility.
The invention provides an analysis method of a stabilizer, which comprises the following steps: detecting the sample by high performance liquid chromatography under the following chromatographic conditions: the stationary phase is octadecylsilane chemically bonded chromatographic column, and the mobile phase A is acidic aqueous solution; the mobile phase B is methanol, the mobile phase C is acetonitrile, and the gradient elution is carried out, wherein the specific program of the gradient elution is as follows: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 29-31:50:19-21; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 14-16:70:14-16 at constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 4-6:85:9-11 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept to be 4-6:85:9-11; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 29-31:50:19-21 at a constant speed within 12.0-13.0 min;
wherein the stabilizer is at least one of hydroquinone, p-hydroxyanisole, p-tert-butylcatechol, phenothiazine, 2, 4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-butyl-p-methylphenol and 2,2' -methylenebis (6-tert-butyl-4-methylphenol).
Preferably, the specific procedure for gradient elution is: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 30:50:20; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 15:70:15 at a constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 5:85:10 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 5:85:10; and the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 30:50:20 at a constant speed within 12.0-13.0 min.
The assay of the present invention may be used to detect one of the 7 stabilizers alone or at least two of the stabilizers together. The method can be used for detecting the test sample to determine whether the test sample contains the stabilizing agents, and can also be used for detecting the content of each stabilizing agent in the test sample.
The CAS number of the hydroquinone is 123-31-9; the CAS number of the p-hydroxyanisole is 150-76-5; the CAS number of the p-tertiary butyl catechol is 98-29-3; the CAS number of the phenothiazine is 92-84-2; the CAS number of the 2, 4-dimethyl-6-tertiary butyl phenol is 1879-09-0; the CAS number of the 2, 6-di-tert-butyl p-methylphenol is 128-37-0; the CAS number for 2,2' -methylenebis (6-tert-butyl-4-methylphenol) is 119-47-1. Are commercially available.
The mobile phase A, the mobile phase B and the mobile phase C are filtered by a filter membrane with the aperture less than or equal to 0.45 mu m and then are used; the influence of bubbles, impurities, microorganisms and the like in the mobile phase on the high performance liquid chromatographic instrument and the detection result can be avoided.
Preferably, in the acidic aqueous solution, the acidic substance is at least one of formic acid, acetic acid, sulfuric acid, phosphoric acid and perchloric acid.
Preferably, in the acidic aqueous solution, the acidic substance is phosphoric acid.
Preferably, in the acidic aqueous solution, the volume fraction of the acidic substance is less than or equal to 0.2%. The pH of the acidic aqueous solution is 2-7.
Preferably, the chromatographic column has a length of 250mm, an inner diameter of 4.6mm and a packing particle size of 5.0. Mu.m.
Preferably, the detector is a VWD detector or a DAD detector.
The VWD detector and DAD detector are commonly used for high performance liquid chromatography detection.
Preferably, when the detector is a VWD detector, the detection wavelength is 278-282nm within 0-7.5 min; the detection wavelength is 247-251nm within 7.51-9.0min, and 278-282nm within 9.01-13.0 min; the flow rate is 0.8ml/min within 0-4.0min, the flow rate is 4.01-5.0min, the flow rate is gradually changed to 1.0ml/min within 5.01-13.0min, and the flow rate is 1.0ml/min.
Preferably, when the detector is a DAD detector, parallel detection is carried out by adopting double wavelengths, wherein the first wavelength is 278-282nm, and the second wavelength is 247-251nm; the constant flow rate is 0.8-1.2ml/min.
The inventor sets 2 detection wavelengths for the detection of 7 stabilizers because the stabilizers of hydroquinone, p-hydroxyanisole, p-tert-butylcatechol, phenothiazine, 2, 4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-butyl-p-methylphenol and 2,2' -methylenebis (6-tert-butyl-4-methylphenol) have maximum absorption peaks at 249nm and the rest stabilizers have maximum absorption peaks at 280nm; phenothiazine is calculated as the peak area at 249nm wavelength, and the remaining 6 stabilizers are calculated as the peak area at 280nm wavelength.
Preferably, the column temperature is 20-35 ℃.
According to the invention, 7 stabilizers can be effectively separated by selecting proper stationary phase, mobile phase and gradient elution program, the separation degree is more than 1.5, the retention time of each stabilizer is within 12min, the detection time is short, and the rapid detection can be realized. By selecting a proper temperature and flow rate of the chromatographic column, the separation degree between the chromatographic peaks can be further improved, and the peak type can be improved.
Preferably, the sample injection amount is 5-15 mu L.
The invention can detect various samples, and the preferred sample is acrylic acid (ester), for example, the sample can be: butyl acrylate, methyl methacrylate, butyl methacrylate, and the like.
Acrylic acid (esters) refers to the generic term for esters of acrylic acid and its homologs. Can self-polymerize or copolymerize with other monomers, and is a monomer for manufacturing adhesive, synthetic resin, special rubber and plastics.
Preferably, the acrylic acid (ester) is diluted with an organic solvent, filtered, and then subjected to high performance liquid chromatography. The pore diameter of the filtering membrane is less than or equal to 0.45 mu m.
The organic solvent may be any organic solvent which does not interfere with the detection of the sample, and may be methanol, ethanol, isopropanol, acetonitrile, or the like, and when the sample is acrylic acid (ester), methanol is preferably used for dissolution and dilution.
The invention can qualitatively or quantitatively detect the stabilizer in the test sample.
The qualitative detection method is a conventional method in the field, and the steps are generally as follows: preparing blank solvent, reference substance solution and test substance solution respectively, sequentially injecting and recording high performance liquid chromatogram, and determining whether the test substance contains the 7 stabilizers according to peak positions in the reference substance solution chromatograms and each chromatographic peak in the test substance chromatograms.
The quantitative detection method can calculate the content of the stabilizer in the test sample by adopting a reference linear regression equation, and generally comprises the following steps: preparing a blank solvent, stepwise diluted reference substance solutions with different concentrations and a test substance solution respectively, sequentially injecting samples and recording a liquid chromatogram, drawing a standard curve by taking the peak area as an ordinate and the concentration of each reference substance as an abscissa, obtaining a linear regression equation of each reference substance, and calculating the content of each stabilizer in the test substance according to the peak area of the test substance solution.
The beneficial effects are that:
according to the invention, 7 stabilizers can be effectively separated by selecting proper chromatographic conditions, the separation degree is more than 1.5, each chromatographic peak type is good, the retention time of each stabilizer is within 12min, the detection time is short, the rapid detection can be realized, the treatment of a sample is simple, and the operation is convenient; the invention has high sensitivity and good reproducibility.
Drawings
FIG. 1 is a high performance liquid chromatogram of a system applicability solution, wherein HQ is hydroquinone, MEHQ is para-hydroxyanisole, TBC is para-tert-butylcatechol, PTA is phenothiazine, TBX is 2, 4-dimethyl-6-tert-butylphenol, BHT is 2, 6-di-tert-butyl-p-methylphenol, and MBP is 2,2' -methylenebis (6-tert-butyl-4-methylphenol).
FIG. 2 is a high performance liquid chromatography of a methyl methacrylate solution in example 3, wherein 1 is methyl methacrylate, 2 is Phenothiazine (PTA), and 3 is 2, 4-dimethyl-6-t-butylphenol (TBX).
FIG. 3 is a high performance liquid chromatogram of a butyl acrylate solution in example 3, wherein 1 is para-hydroxyanisole (MEHQ) and 2 is butyl acrylate.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1 (Peak positioning experiment)
A method of analyzing a stabilizer comprising the steps of:
the detection is carried out by using an Agilent 1260 high performance liquid chromatograph, the detector is a VWD detector, and the chromatographic conditions are as follows:
the chromatographic column is ZORBAX SC-C18 chromatographic column (250 mm×4.6mm,5.0 μm), the chromatographic column temperature is 23deg.C, and mobile phase A is 0.1% phosphoric acid water solution by volume fraction; the mobile phase B is methanol, the mobile phase C is acetonitrile, and the gradient elution is carried out, wherein the specific program of the gradient elution is as follows: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 30:50:20; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 15:70:15 at a constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 5:85:10 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 5:85:10; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 30:50:20 at a constant speed within 12.0-13.0 min;
within 0-8.0min, the detection wavelength is 280nm; the detection wavelength is 249nm within 8.01-9.0min, and 280nm within 9.01-13.0 min;
the flow rate is 0.8ml/min within 0-4.0min, the flow rate is 4.01-5.0min, the flow rate is gradually changed to 1.0ml/min within 5.01-13.0min, and the flow rate is 1.0ml/min.
Preparing a solution:
blank solution: methanol.
Hydroquinone control solution: taking a proper amount of hydroquinone reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare a solution containing 493 mug of hydroquinone reference substance in each 1 ml.
Para-hydroxyanisole control solution: taking a proper amount of para-hydroxyanisole reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare 539 mug of para-hydroxyanisole reference substance solution in each 1 ml.
Para-tertiary butyl catechol control solution: and (3) taking a proper amount of the para-tertiary butyl catechol reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare a solution containing 503 mug of the para-tertiary butyl catechol reference substance in each 1 ml.
Phenothiazine control solution: taking a proper amount of phenothiazine reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare 494 mug of phenothiazine reference substance in each 1ml of the solution.
2, 4-dimethyl-6-tert-butylphenol control solution: taking a proper amount of 2, 4-dimethyl-6-tertiary butyl phenol reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare a solution containing 601 mug of the 2, 4-dimethyl-6-tertiary butyl phenol reference substance in each 1 ml.
2, 6-Di-tert-butyl p-methylphenol control solution: taking a proper amount of 2, 6-di-tert-butyl-p-methylphenol reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare 529 mu g of solution containing the 2, 6-di-tert-butyl-p-methylphenol reference substance in each 1 ml.
2,2' -methylenebis (6-tert-butyl-4-methylphenol) control solution: taking a proper amount of 2,2 '-methylenebis (6-tertiary butyl-4-methylphenol) reference substance, precisely weighing, and quantitatively diluting with a blank solution to prepare a solution containing 516 mug of the 2,2' -methylenebis (6-tertiary butyl-4-methylphenol) reference substance in each 1 ml.
System applicability solution: the hydroquinone reference solution, the p-hydroxyanisole reference solution, the p-tert-butylcatechol reference solution, the phenothiazine reference solution, the 2, 4-dimethyl-6-tert-butylphenol reference solution, the 2, 6-di-tert-butylp-methylphenol reference solution and the 2,2 '-methylenebis (6-tert-butyl-4-methylphenol) reference solution are respectively and properly measured, and the mixed solution containing 78.88 mug of the hydroquinone reference, 86.24 mug of the p-hydroxyanisole reference, 80.48 mug of the p-tert-butylcatechol reference, 79.04 mug of the phenothiazine reference, 96.16 mug of the 2, 4-dimethyl-6-tert-butylphenol reference, 84.64 mug of the 2, 6-di-tert-butyl-p-methylphenol reference and 82.72 mug of the 2,2' -methylenebis (6-tert-butyl-4-methylphenol) reference is prepared by quantitatively diluting the blank solution.
The operation is as follows:
taking blank solvent, each reference substance solution and system applicability solution, respectively injecting 5 mu L of sample, and recording a chromatogram. The results are shown in FIG. 1 and Table 1. FIG. 1 is a high performance liquid chromatogram of a system applicability solution, wherein HQ is hydroquinone, MEHQ is para-hydroxyanisole, TBC is para-tert-butylcatechol, PTA is phenothiazine, TBX is 2, 4-dimethyl-6-tert-butylphenol, BHT is 2, 6-di-tert-butyl-p-methylphenol, and MBP is 2,2' -methylenebis (6-tert-butyl-4-methylphenol).
Table 1 results of determination of retention time and separation degree of each component
Remarks: the result of phenothiazine is the result of detection at 249nm, and the result of detection of the other 6 stabilizers is the result of detection at 280 nm.
As can be seen from table 1 and fig. 1, the components in the system applicability solution are completely separated.
Example 2 (Linear test, detection Limit and quantitative Limit)
The analysis conditions were the same as in example 1.
Preparing a solution:
weighing a proper amount of hydroquinone reference substance, p-hydroxyanisole reference substance, p-tert-butylcatechol reference substance, phenothiazine reference substance, 2, 4-dimethyl-6-tert-butylphenol reference substance, 2, 6-di-tert-butyl-p-methylphenol reference substance and 2,2' -methylenebis (6-tert-butyl-4-methylphenol) reference substance, gradually diluting with a blank solution into a series of mixed solutions with different concentrations, respectively taking 5 mu L of each mixed solution, sequentially detecting, taking the sample concentration at a signal-to-noise ratio of about 3 as a detection limit, and taking the sample concentration at a signal-to-noise ratio of about 10 as a quantitative limit. And examining the linear relationship of the analysis method of the present invention. The results are shown in Table 2.
TABLE 2 detection results
Remarks: the result of phenothiazine is the result of detection at 249nm, and the result of detection of the other 6 stabilizers is the result of detection at 280 nm.
As can be seen from Table 2, the linear relationship was good between hydroquinone and p-hydroxyanisole in the concentration range of 4.93-259.8. Mu.g/ml, the linear relationship was good between p-hydroxyanisole in the concentration range of 5.39-323.4. Mu.g/ml, the linear relationship was good between p-tert-butylcatechol in the concentration range of 5.03-301.8. Mu.g/ml, the linear relationship was good between phenothiazine in the concentration range of 4.94-296.4. Mu.g/ml, the linear relationship was good between 2, 4-dimethyl-6-tert-butylphenol in the concentration range of 6.01-360.6. Mu.g/ml, the linear relationship was good between 2, 6-di-tert-butyl-p-methylphenol in the concentration range of 5.29-317.4. Mu.g/ml, and the linear relationship was good between 2,2' -methylenebis (6-tert-butyl-4-methylphenol) in the concentration range of 5.18-310.8. Mu.g/ml. The analytical method of the invention has high sensitivity.
Example 3
The analysis conditions were the same as in example 1.
Preparing a solution:
blank solution: methanol.
Linear solution: weighing a proper amount of hydroquinone reference substance, p-hydroxyanisole reference substance, p-tert-butylcatechol reference substance, phenothiazine reference substance, 2, 4-dimethyl-6-tert-butylphenol reference substance, 2, 6-di-tert-butyl-p-methylphenol reference substance and 2,2' -methylenebis (6-tert-butyl-4-methylphenol) reference substance, and gradually diluting with a blank solution to obtain a series of mixed solutions with different concentrations.
Methyl methacrylate solution: a proper amount of methyl methacrylate, precisely 1.1764g, was taken and placed in a 10ml measuring flask, diluted to the scale with a blank solution and shaken well.
Butyl acrylate solution: a proper amount of butyl acrylate is taken, precisely named 1.2056g, placed in a 10ml measuring flask, diluted to the scale with a blank solution and shaken well.
The operation is as follows:
taking a blank solvent, a linear solution, a methyl methacrylate solution and a butyl acrylate solution, respectively injecting 5 mu L of sample, and recording a chromatogram. The result of phenothiazine is the result of detection at 249nm, and the result of detection of the other 6 stabilizers is the result of detection at 280 nm.
Obtaining a linear regression equation of each reference substance according to the linear solution, and measuring the concentration of each stabilizer in methyl methacrylate and butyl acrylate according to the linear regression equation of each reference substance, thereby further calculating that the content of Phenothiazine (PTA) in methyl methacrylate is 0.0071%, the content of 2, 4-dimethyl-6-tertiary butyl phenol (TBX) is 0.028%, and other stabilizers are not detected; the content of para-hydroxyanisole (MEHQ) in butyl acrylate was 0.0086%, and other stabilizers were not detected. Typical chromatograms are shown in FIGS. 2-3.
FIG. 2 is a high performance liquid chromatography of a methyl methacrylate solution in example 3, wherein 1 is methyl methacrylate, 2 is Phenothiazine (PTA), and 3 is 2, 4-dimethyl-6-t-butylphenol (TBX).
FIG. 3 is a high performance liquid chromatogram of a butyl acrylate solution in example 3, wherein 1 is para-hydroxyanisole (MEHQ) and 2 is butyl acrylate.
Example 4
A method of analyzing a stabilizer comprising the steps of:
the detection is carried out by using an Agilent 1260 high performance liquid chromatograph, the detector is a DAD detector, and the chromatographic conditions are as follows:
the chromatographic column is ZORBAX SC-C18 chromatographic column (250 mm×4.6mm,5.0 μm), the temperature of the chromatographic column is 25deg.C, and the mobile phase A is 0.05% formic acid water solution by volume fraction; the mobile phase B is methanol, the mobile phase C is acetonitrile, and the gradient elution is carried out, wherein the specific program of the gradient elution is as follows: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 29:50:21; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 15:70:15 at a constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 4:85:11 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 4:85:11; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 29:50:21 at a constant speed within 12.0-13.0 min;
the constant flow rate was 0.9ml/min, and parallel detection was performed using dual wavelengths, the first wavelength being 280nm and the second wavelength being 249nm.
Solution formulation and operation were as in example 3. The result of phenothiazine is the result of detection at 249nm, and the result of detection of the other 6 stabilizers is the result of detection at 280 nm.
The content of Phenothiazine (PTA) in methyl methacrylate was 0.0070%, the content of 2, 4-dimethyl-6-t-butylphenol (TBX) was 0.028%, and other stabilizers were not detected;
the content of para-hydroxyanisole (MEHQ) in butyl acrylate was 0.0085%, and other stabilizers were not detected.
Example 5
A method of analyzing a stabilizer comprising the steps of:
the detection is carried out by using an Agilent 1260 high performance liquid chromatograph, the detector is a DAD detector, and the chromatographic conditions are as follows:
the chromatographic column is ZORBAX SC-C18 chromatographic column (250 mm×4.6mm,5.0 μm), the chromatographic column temperature is 30deg.C, and mobile phase A is 0.2% formic acid water solution; the mobile phase B is methanol, the mobile phase C is acetonitrile, and the gradient elution is carried out, wherein the specific program of the gradient elution is as follows: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 30:50:20; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 15:70:15 at a constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 6:85:9 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 6:85:9; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 30:50:20 at a constant speed within 12.0-13.0 min;
the constant flow rate was 1.05ml/min, parallel detection was performed using dual wavelengths, the first wavelength being 280nm and the second wavelength being 249nm.
Solution formulation and operation were as in example 3. The result of phenothiazine is the result of detection at 249nm, and the result of detection of the other 6 stabilizers is the result of detection at 280 nm.
The content of Phenothiazine (PTA) in methyl methacrylate was 0.0071%, the content of 2, 4-dimethyl-6-t-butylphenol (TBX) was 0.028%, and other stabilizers were not detected;
the content of para-hydroxyanisole (MEHQ) in butyl acrylate was 0.0085%, and other stabilizers were not detected.
The production lot of methyl methacrylate and the production lot of butyl acrylate in examples 3 to 5 were the same.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (13)
1. A method of analyzing a stabilizer, comprising the steps of: detecting the sample by high performance liquid chromatography under the following chromatographic conditions: the stationary phase is octadecylsilane chemically bonded chromatographic column, and the mobile phase A is acidic aqueous solution; the mobile phase B is methanol, the mobile phase C is acetonitrile, and the gradient elution is carried out, wherein the specific program of the gradient elution is as follows: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 29-31:50:19-21; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 14-16:70:14-16 at constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 4-6:85:9-11 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept to be 4-6:85:9-11; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 29-31:50:19-21 at a constant speed within 12.0-13.0 min;
wherein the stabilizer is hydroquinone, p-hydroxyanisole, p-tert-butylcatechol, phenothiazine, 2, 4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-butyl-p-methylphenol and 2,2' -methylenebis (6-tert-butyl-4-methylphenol).
2. The method for analyzing a stabilizer according to claim 1, wherein the specific procedure of the gradient elution is: within 0-4.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 30:50:20; the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 15:70:15 at a constant speed within 4.0-5.0 min; in 5.0-6.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 5:85:10 at constant speed; within 6.0-12.0min, the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is kept at 5:85:10; and the volume ratio of the mobile phase A to the mobile phase B to the mobile phase C is gradually changed to 30:50:20 at a constant speed within 12.0-13.0 min.
3. The method according to claim 1, wherein the acidic substance in the acidic aqueous solution is at least one of formic acid, acetic acid, sulfuric acid, phosphoric acid, and perchloric acid.
4. The method for analyzing a stabilizer according to claim 1, wherein the acidic substance is phosphoric acid in the acidic aqueous solution.
5. The method according to claim 3 or 4, wherein the volume fraction of the acidic substance in the acidic aqueous solution is not more than 0.2%.
6. The method for analyzing a stabilizer according to claim 1, wherein the column has a length of 250mm, an inner diameter of 4.6mm, and a filler particle diameter of 5.0. Mu.m.
7. The method of claim 1, wherein the detector is a VWD detector or a DAD detector.
8. The method of claim 7, wherein the detection wavelength is 278-282nm within 0-7.5min when the detector is a VWD detector; the detection wavelength is 247-251nm within 7.51-9.0min, and 278-282nm within 9.01-13.0 min; the flow rate is 0.8ml/min within 0-4.0min, the flow rate is 4.01-5.0min, the flow rate is gradually changed to 1.0ml/min within 5.01-13.0min, and the flow rate is 1.0ml/min.
9. The method according to claim 7, wherein when the detector is a DAD detector, the parallel detection is performed using two wavelengths, the first wavelength is 278-282nm, and the second wavelength is 247-251nm; the constant flow rate is 0.8-1.2ml/min.
10. The method of claim 1, wherein the chromatographic column temperature is 20-35 ℃.
11. The method for analyzing a stabilizer according to claim 1, wherein the amount of the sample is 5 to 15. Mu.L.
12. The method for analyzing a stabilizer according to claim 1, wherein the test substance is acrylic acid (ester).
13. The method according to claim 12, wherein the method comprises diluting the acrylic acid (ester) with an organic solvent, filtering, and performing high performance liquid chromatography.
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Effective date of registration: 20231018 Address after: 239000, No. 68, Shuangmiao Road, Wuyi Town, Chuzhou City, Anhui Province (in Anhui Zhongxing new material Co., Ltd.) Patentee after: ANHUI ZHONGBO NEW MATERIALS CO.,LTD. Address before: 239000 no.2188 fengle Avenue, Chuzhou City, Anhui Province Patentee before: CHUZHOU VOCATIONAL AND TECHNICAL College |