CN109061026B - Method for analyzing and detecting synthesized PEEK sample - Google Patents
Method for analyzing and detecting synthesized PEEK sample Download PDFInfo
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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
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- G01N30/02—Column chromatography
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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
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- G—PHYSICS
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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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- 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
- G01N2030/146—Preparation by elimination of some components using membranes
Abstract
The invention relates to a method for analyzing and detecting a synthesized PEEK sample, which comprises the following steps: s11, preparing a high performance liquid chromatograph provided with an ultraviolet detector and a chromatographic column, setting the mobile phase parameters of acetonitrile/pure water =65/35 isocratic elution, the column temperature is 30 ℃, and the wavelength of the ultraviolet detector is 235 nm; s12, mixing acetonitrile and pure water according to a volume ratio of 65/35 to obtain a mobile phase; s13, preparing standard samples with different concentrations by respectively taking hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone through flow matching; s14, diluting the object to be measured with known mass with mobile phase to obtain a sample of solution to be measured; s15, after the instrument is stabilized, injecting a sample for analysis, wherein the peak sequences are hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone, and recording each absorption peak; and S16, fitting an absorption peak area and a concentration-absorbance standard curve of the standard solution, and calculating the contents of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in the substance to be detected by using the peak area and the dilution times. The method is rapid and has good repeatability.
Description
Technical Field
The invention relates to a chemical analysis method, in particular to a method for analyzing and detecting a synthesized PEEK sample.
Background
Polyether Ether Ketone (PEEK resin for short), namely PEEK is a high polymer consisting of repeating units containing one Ketone bond and two Ether bonds in a main chain structure, and belongs to a special high polymer material. The high-temperature-resistant and chemical-corrosion-resistant composite material has physical and chemical properties such as high temperature resistance and chemical corrosion resistance, is a crystalline high polymer material, has a melting point of 334 ℃, a softening point of 168 ℃ and a tensile strength of 132-148 MPa, can be used as a high-temperature-resistant structural material and an electrical insulating material, and can be compounded with glass fibers or carbon fibers to prepare a reinforcing material. The PEEK has excellent comprehensive performance, so that the PEEK can replace traditional materials such as metal, ceramics and the like in many special fields. The plastic has the characteristics of high temperature resistance, self lubrication, wear resistance, fatigue resistance and the like, so that the plastic becomes one of the most popular high-performance engineering plastics at present, and is mainly applied to the fields of aerospace, automobile industry, electronics, electrical and medical appliances and the like.
PEEK is prepared from 4, 4' -difluorobenzophenone and hydroquinone through condensation reaction in the presence of alkali carbonate and diphenyl sulfone as solvent. A simple PEEK was synthesized as follows:
after the reaction process for synthesizing PEEK in industrial production or laboratories is finished, the components in the reaction system for synthesizing PEEK are required to be quantitatively detected and analyzed, the yield of the reaction is calculated, and the molecular weight of the polymer PEEK is measured for controlling and researching the reaction process.
However, there is only a few literature reports that the contents of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in the reaction system for synthesizing PEEK can be simultaneously detected by one method. Jinyushun uses ultraviolet spectroscopy to determine diphenyl sulfone in the synthesis and purification of polyether-ether-ketone; royal courage in "research progress of methods for detecting catechol and hydroquinone in Water" has described methods for detecting hydroquinone, such as chromatography, spectrophotometer and electrochemical method, wherein the chromatography has high accuracy and good sensitivity; the content of 4, 4' -difluorobenzophenone is determined by a gas phase method. Therefore, at present, a test method capable of simultaneously detecting the contents of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in a reaction system for synthesizing PEEK is provided.
In addition, the molecular weight of the product PEEK is also difficult to determine after the reaction to synthesize PEEK is complete. PEEK materials have excellent chemical resistance, are unaffected by many organic and inorganic chemicals, and are only soluble in strong or anhydrous oxidants. Deviaux, D.Delimoy test method for analyzing the molecular weight of PEEK requires running in a mixture of trichlorobenzene and phenol at an elevated temperature of 115 ℃ and Analysis of Polymers by GPC/SEC energy & ChemiCAl APPLICATIONS describes a method of testing the molecular weight of PEEK using a mixed solvent of dichloroacetic acid and trichloromethane. In the two test methods, the former has strict requirements on instruments and is not environment-friendly in mobile phase (trichlorobenzene can be absorbed by skin and has high toxicity, phenol is a WHO (general health organization) and is listed as a 3-class carcinogen), the latter has no detailed requirements on temperature and is not environment-friendly in trichloromethane, and the trichloromethane can be decomposed with oxygen in the air to generate virulent phosgene (carbonyl chloride) and hydrogen chloride when being exposed to light.
Disclosure of Invention
Objects of the invention
In order to solve the problems in the prior art, the invention aims to provide a method for analyzing and detecting a synthesized PEEK sample, which can simultaneously measure the content of three substances, namely hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in the PEEK.
Further, the method further comprises measuring the molecular weight of the synthesized PEEK, and understanding the molecular weight size and polymerization degree of the synthesized PEEK.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
a method for analyzing and detecting a synthesized PEEK sample comprises a method for detecting the contents of hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone in a reaction system, wherein the method comprises the following operation steps:
s11, preparing a high performance liquid chromatograph provided with an ultraviolet detector and a chromatographic column, adjusting the sample injection amount to 5 mu L, setting the mobile phase parameter to be equal elution of 65/35 acetonitrile/pure water, setting the flow rate to be 1.0mL/min, setting the column temperature to be 30 ℃, and setting the wavelength of the ultraviolet detector to be 235 nm;
s12, mixing acetonitrile and pure water according to a volume ratio of 65/35 to prepare a mobile phase;
s13, preparing a proper amount of standard substances of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone into standard substance solution samples with different concentrations by using a mobile phase for later use so as to obtain a concentration-absorbance standard curve;
s14, taking the object to be measured with known quality, diluting the object to be measured into a solution sample to be measured by the prepared mobile phase according to a certain dilution multiple, and filtering the solution sample for later use;
s15, setting sequence parameters, carrying out sample injection analysis after the high performance liquid chromatograph is stabilized, sequentially recording absorption peaks of hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone in the order of the peak output of the solution sample to be detected by an ultraviolet detector;
and S16, fitting an absorption peak area and a concentration-absorbance standard curve of a standard solution sample, and respectively calculating the contents of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in the substance to be detected by using the peak area and the dilution times.
Preferably, the chromatographic column is a C18 reverse phase column.
Preferably, in step S13, the standard solution sample concentration includes 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500 mg/L.
Preferably, in step S14, 4g ± 0.2g of the analyte is taken, and the volume is determined to be 100mL volumetric flask by mobile phase, so as to prepare the sample of the analyte solution, and the sample is filtered by an organic filter membrane for standby.
The method also comprises a method for detecting the molecular weight of the PEEK synthesized in the reaction system, and the method comprises the following operation steps:
s21, preparing a gel permeation chromatograph equipped with a differential detector and a gel chromatographic column, setting the quantitative loop to be 25 mu L, the sample injection amount to be 20-40 mu L, the mobile phase parameter to be equal-degree elution of 7/3-9/1 of dichloroacetic acid/dichloromethane, setting the flow rate to be 0.7-1.0 mL/min, the column temperature to be 30 ℃, and the analysis time: not less than 30 min;
s22, mixing dichloroacetic acid and dichloromethane according to a volume ratio of 7/3-9/1 to prepare a mobile phase;
s23, respectively dissolving three high molecular polymer standard substances with different weight average molecular weights Mw into a mobile phase to prepare a standard solution sample of 10mg/mL for later use so as to obtain a linear regression equation;
s24, dissolving the product PEEK with known mass in a mobile phase to prepare a solution sample to be detected with the mass fraction of 2 per mill, and filtering for later use;
s25, after the gel permeation chromatograph is stabilized, sample introduction and analysis are carried out on a standard solution sample, a differential chromatogram is recorded, a standard curve is drawn by special GPC software, and the linear regression equation is that logMw is a + bRT;
wherein Mw is the known weight average molecular weight of the standard solution sample, and RT is the retention time of the standard solution sample;
s26, then, carrying out sample injection analysis on the solution sample to be detected, recording a differential chromatogram, and calculating the molecular weight by combining a linear regression equation as follows:
weight average molecular weight Mw ═ Σ (RIi × Mi)/Σ RIi;
number average molecular weight Mn ═ Σ RIi/Σ (RIi/Mi);
the dispersion coefficient D is Mw/Mn;
wherein RIi is the peak height of the differential chromatogram of the solution sample to be detected, and Mi is the molecular weight obtained by substituting the time point i of the differential chromatogram of the solution sample to be detected into the standard curve.
Preferably, in step S23, M is usedW193000Da, 42600Da, 16200Da polystyrene standard.
Preferably, in step S21, the gel column is of type Agilent MIXED-B, 300 mm. times.7.5 mm, 10 μm, and is used in 2 number.
Preferably, in step S24, the sample is first dissolved in 1% solution at 150 ℃ with dichloroacetic acid, and then diluted with dichloromethane to 2 ‰ sample solution, and filtered through an organic filter membrane for further use.
Preferably, steps S25-S26 are performed by running dedicated program software.
It should be noted that the method for detecting the molecular weight of PEEK of the present invention does not depend on the method for detecting the contents of hydroquinone, diphenylsulfone, and 4, 4-difluorobenzophenone contained in the reaction system, in other words, the two methods can be used in one set of detection scheme or can be separately used.
(III) advantageous effects
The invention has the beneficial effects that:
the method can rapidly and simultaneously detect the content of each of three raw materials (hydroquinone, 4' -difluorobenzophenone and diphenyl sulfone) in a reaction system for synthesizing PEEK, and has the advantages of simple operation, good repeatability, small relative deviation and high stability; the temperature of the chromatographic column is 30 ℃ in the detection process, so the requirement on the instrument is low.
The method can quickly detect the weight average molecular weight and the number average molecular weight of the PEEK material, has simple and quick operation and high stability, uses more environment-friendly solvent (mobile phase), has the operation temperature close to normal temperature and has lower requirements on instruments.
Drawings
FIG. 1 is a liquid chromatogram of hydroquinone, 4, 4' -difluorobenzophenone and diphenyl sulfone sequentially obtained by sampling PEEK and detecting the PEEK by a high performance liquid chromatograph equipped with an ultraviolet detector.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The following examples 1 to 4 are specific examples of the method for detecting the content of three substances, hydroquinone, 4, 4' -difluorobenzophenone and diphenyl sulfone, which are residual reaction raw materials in PEEK.
Example 1
(1) A high performance liquid chromatograph equipped with an ultraviolet detector was prepared, and the column was AQ-C18.
(2) Setting the experimental conditions: the sample injection amount is 5 mu L; mobile phase: isocratic elution, a/B-65/35, where a phase is acetonitrile, B phase is water, detector wavelength: 235 nm; flow rate: 1.0 mL/min; column temperature: 30 ℃; analysis time: and (4) 18 min.
(3) And (3) preparing a mobile phase A/B-65/35, wherein the phase A is acetonitrile, and the phase B is water.
(4) Taking a proper amount of hydroquinone standard substance, and preparing standard solution samples of 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500mg/L by using mobile phase.
(5) 4.0197g of PEEK sample is taken and added into a volumetric flask with 100mL of constant volume by a mobile phase to prepare a sample solution to be detected, and the sample solution is filtered by an organic filter membrane for standby.
(6) Setting sequence parameters, and starting sample introduction after the instrument is stable. The peak position of hydroquinone is 2.91min, the standard curve is that y is 3.782x +16.638, R20.9994. The hydroquinone content of the sample was calculated according to the standard curve to be 47.24 mg/g.
Example 2
(1) A high performance liquid chromatograph equipped with an ultraviolet detector was prepared, and the column was AQ-C18.
(2) Setting the experimental conditions: the sample injection amount is 5 mu L; mobile phase: isocratic elution, a/B-65/35, where a phase is acetonitrile, B phase is water, detector wavelength: 235 nm; flow rate: 1.0 mL/min; column temperature: 30 ℃; analysis time: and (4) 18 min.
(3) And (3) preparing a mobile phase A/B-65/35, wherein the phase A is acetonitrile, and the phase B is water.
(4) Taking a proper amount of standard substance of diphenyl sulfone, and preparing standard solution samples of 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500mg/L by using mobile phase.
(5) 4.0197g of PEEK sample is taken and added into a volumetric flask with 100mL of constant volume by a mobile phase to prepare a sample solution to be detected, and the sample solution is filtered by an organic filter membrane for standby.
(6) Setting sequence parameters, and starting sample introduction after the instrument is stable. The peak position of diphenyl sulfone is 5.76min, the standard curve is y ═ 19.578x +23.921, R21. The diphenylsulfone content 328.35 in the sample was calculated from the standard curvemg/g。
Example 3
(1) A high performance liquid chromatograph equipped with an ultraviolet detector was prepared, and the column was AQ-C18.
(2) Setting the experimental conditions: the sample injection amount is 5 mu L; mobile phase: isocratic elution, a/B-65/35, where a phase is acetonitrile, B phase is water, detector wavelength: 235 nm; flow rate: 1.0 mL/min; column temperature: 30 ℃; analysis time: and (4) 18 min.
(3) And (3) preparing a mobile phase A/B-65/35, wherein the phase A is acetonitrile, and the phase B is water.
(4) Taking a proper amount of 4, 4' -difluorobenzophenone standard substance, and preparing standard solution samples of 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500mg/L by using mobile phase.
(5) 4.0197g of PEEK sample is taken and added into a volumetric flask with 100mL of constant volume by a mobile phase to prepare a sample solution to be detected, and the sample solution is filtered by an organic filter membrane for standby.
(6) Setting sequence parameters, and starting sample introduction after the instrument is stable. The peak time of 4, 4' -difluorobenzophenone is 8.9min, and the standard curve is that y is 7.9916x +7.5675, R21. The content of 4, 4' -difluorobenzophenone in the sample was calculated according to the standard curve as 672.61 mg/g.
Example 4
(1) A high performance liquid chromatograph equipped with an ultraviolet detector was prepared, and the column was AQ-C18.
(2) Setting the experimental conditions: the sample injection amount is 5 mu L; mobile phase: isocratic elution, a/B-65/35, where a phase is acetonitrile, B phase is water, detector wavelength: 235 nm; flow rate: 1.0 mL/min; column temperature: 30 ℃; analysis time: and (4) 18 min.
(3) And (3) preparing a mobile phase A/B-65/35, wherein the phase A is acetonitrile, and the phase B is water.
(4) Taking appropriate amounts of hydroquinone standard substance, 4' -difluorobenzophenone standard substance and diphenylsulfone standard substance, respectively, and diluting with mobile phase to obtain standard solution samples of 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500 mg/L.
(5) 4.0200g of PEEK sample is taken and added into a volumetric flask with 100mL of constant volume by a mobile phase to prepare a sample solution to be detected, and the sample solution is filtered by an organic filter membrane for standby.
(6) Setting sequence parameters, sampling samples for 6 times, and starting sampling after the instrument is stable. Wherein, the appearance sequence of the sample solution to be detected is as follows in sequence: hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone as shown in figure 1. The peak emergence time of hydroquinone, 4' -difluorobenzophenone and diphenyl sulfone is 2.91min, 8.9min and 5.76min in sequence. The peak area of the standard solution sample of 2mg/L is obviously different from the peak area change trend of other concentrations. Therefore, corresponding standard curves are made for 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500mg/L of standard solution samples, the hydroquinone concentration-absorbance curve is that y is 3.782x +16.638, R is20.9994; the diphenyl sulfone concentration-absorbance curve is: 19.578x +23.921, R21 is ═ 1; the concentration-absorbance curve of 4, 4' -difluorobenzophenone is that y is 7.9916x +7.5675, R2＝1。
(7) According to the standard curve, the contents of hydroquinone, 4, 4' -difluorobenzophenone and diphenyl sulfone in the sample are respectively 47.05mg/g, 328.10mg/g and 672.48 mg/g. RSD% is 0.3%, 0.08% and 0.08% in sequence, and the detection limit reaches 5 mg/L. Specific data are shown in table 1 below.
TABLE 1 repeated experimental data for PEEK sample 20180323
The following examples 5 to 9 are specific examples of the method for detecting the molecular weight of PEEK in a PEEK sample.
Example 5
(1) A gel chromatograph equipped with a differential detector was prepared, and the column was Agilent MIXED-B, 2 columns.
(2) Setting the experimental conditions: the sample injection amount is 20 mu L; mobile phase: isocratic elution, a/B7: 3, wherein the phase A is dichloroacetic acid, the phase B is dichloromethane, and the flow rate is as follows: 1 mL/min; column temperature: 30 ℃; analysis time: and (3) 30 min.
(3) Preparing a mobile phase A/B volume ratio of 7: 3, wherein the phase A is dichloroacetic acid, and the phase B is dichloromethane.
(4) Diluting the weight average molecular weight with a mobile phaseQuantum MWPolystyrene was prepared at 193000Da, 42600Da, 16200Da, making 10mg/L standard solution samples.
(5) Firstly, dissolving a sample into a 1% solution by using dichloroacetic acid at the temperature of 150 ℃, then diluting the sample by using dichloromethane to prepare a sample solution to be detected with the mass fraction of 2 per mill, and filtering the sample solution by using an organic filter membrane for later use.
(6) After the gel chromatograph is stabilized, manual sample injection is started.
Recording the differential chromatogram of the standard sample solution, drawing a standard curve by special GPC software, and obtaining a linear regression equation with the log molecular weight of 9.1845-0.3042 v.
(7) Sample introduction and analysis are carried out on a solution sample to be detected, a differential chromatogram of the solution sample to be detected is recorded, and the weight average molecular weight M of the sample is calculated by combining a linear regression equation with the log molecular weight of 9.1845-0.3042vWThe number-average molecular weight Mn and the dispersion coefficient D are 81677Da, 38617g/mol, 2118190, respectively.
Example 6
(1) A gel chromatograph equipped with a differential detector was prepared, and the column was Agilent MIXED-B, 2 columns.
(2) Setting the experimental conditions: the sample injection amount is 40 mu L; mobile phase: isocratic elution, a/B9: 1, wherein phase a is dichloroacetic acid and phase B is dichloromethane, flow rate: 1 mL/min; column temperature: 30 ℃; analysis time: and (3) 30 min.
(3) Preparing a mobile phase A/B volume ratio of 9: 1, wherein the phase A is dichloroacetic acid, and the phase B is dichloromethane.
(4) Dilution of the weight-average molecular weight M with a mobile phaseWPolystyrene was prepared at 193000Da, 42600Da, 16200Da, making 10mg/L standard solution samples.
(5) Firstly, dissolving a sample into a 1% solution by using dichloroacetic acid at the temperature of 150 ℃, then diluting the sample by using dichloromethane to prepare a sample solution to be detected with the mass fraction of 2 per mill, and filtering the sample solution by using an organic filter membrane for later use.
(6) And starting manual sample injection after the instrument is stabilized. Recording the differential chromatogram of the standard sample solution, drawing a standard curve by GPC special software, and obtaining a linear regression equation with the log molecular weight of 9.3458-0.313 v.
(7) Will be provided withSample introduction analysis is carried out on a solution sample to be detected, a differential chromatogram of the solution sample to be detected is recorded, and the weight average molecular weight M of the sample is calculated by combining a linear regression equation with the log molecular weight of 9.3458-0.313vWThe number-average molecular weight Mn and the dispersion coefficient are respectively 81600Da, 38601g/mol, 2118123.
Example 7
(1) A gel chromatograph equipped with a differential detector was prepared, and the column was Agilent MIXED-B, 2 columns.
(2) Setting the experimental conditions: the sample injection amount is 40 mu L; mobile phase: isocratic elution, a/B8: 2, wherein phase a is dichloroacetic acid and phase B is dichloromethane, flow rate: 1 mL/min; column temperature: 30 ℃; analysis time: and (3) 30 min.
(3) Preparing a mobile phase A/B volume ratio of 8: 2, wherein the phase A is dichloroacetic acid, and the phase B is dichloromethane.
(4) Dilution of the weight-average molecular weight M with a mobile phaseWPolystyrene was prepared at 193000Da, 42600Da, 16200Da, making 10mg/L standard solution samples.
(5) Firstly, dissolving a sample into a 1% solution by using dichloroacetic acid at the temperature of 150 ℃, then diluting the sample by using dichloromethane to prepare a sample solution to be detected with the mass fraction of 2 per mill, and filtering the sample solution by using an organic filter membrane for later use.
(6) After the gel chromatograph is stabilized, manual sample injection is started.
Recording the differential chromatogram of the standard sample solution, drawing a standard curve by GPC special software, and obtaining a linear regression equation with the log molecular weight of 9.2756-0.3086 v.
(7) Sample introduction analysis is carried out on a solution sample to be detected, a differential chromatogram of the solution sample to be detected is recorded, and the weight average molecular weight M of the sample is calculated by combining a linear regression equationWThe number-average molecular weight Mn and the dispersion coefficient are 81494Da, 38475g/mol, 2118096 respectively.
Example 8
(1) A gel chromatograph equipped with a differential detector was prepared, and the column was Agilent MIXED-B, 2 columns.
(2) Setting the experimental conditions: the sample injection amount is 40 mu L; mobile phase: isocratic elution, a/B8: 2, wherein phase a is dichloroacetic acid and phase B is dichloromethane, flow rate: 0.7 mL/min; column temperature: 30 ℃; analysis time: and (3) 30 min.
(3) Preparing a mobile phase A/B volume ratio of 8: 2, wherein the phase A is dichloroacetic acid, and the phase B is dichloromethane.
(4) Dilution of the weight-average molecular weight M with a mobile phaseWPolystyrene was prepared at 193000Da, 42600Da, 16200Da, making 10mg/L standard solution samples.
(5) Firstly, dissolving a sample into a 1% solution by using dichloroacetic acid at the temperature of 150 ℃, then diluting the sample into a to-be-detected sample solution with the mass fraction of 2 per mill by using dichloromethane, and filtering the to-be-detected sample solution by using an organic filter membrane for later use.
(6) After the gel chromatograph is stabilized, manual sample injection is started. The differential chromatogram of the standard sample solution was recorded. Standard curves were drawn by GPC-specific software with linear regression equations of log molecular weight 10.434-0.3408 v.
(7) Sample introduction analysis is carried out on a solution sample to be detected, a differential chromatogram of the solution sample to be detected is recorded, and the weight average molecular weight M of the sample is calculated by combining a linear regression equationWThe number-average molecular weight Mn and the dispersion coefficient are 81500Da, 38499g/mol, 2118111, respectively.
Table 2 shows the degrees of separation of the eluents of examples 5 to 8 from polystyrene standards having molecular weights of 193000Da, 42600Da and 16200 Da.
| Eluent components and proportions | Flow rate of eluent | Column temperature | Degree of separation |
| Dichloromethane: dichloroacetic acid 3:7 | 1ml/min | 30℃ | 1.5 |
| Dichloromethane: dichloroacetic acid 1:9 | 1ml/min | 30℃ | 1.2 |
| Dichloromethane: dichloroacetic acid 2:8 | 1ml/min | 30℃ | 1.8 |
| Dichloromethane: dichloroacetic acid 2:8 | 0.7ml/min | 30℃ | 2.0 |
As a result, when the eluent is dichloroacetic acid/dichloromethane which is mixed according to the volume ratio of 7/3-9/1, the separation degree of the polystyrene with the molecular weight of 193000Da, 42600Da and 16200Da is better, the peaks of the polystyrene can be completely separated, and the sensitivity and the stability of the detection can be ensured.
Claims (6)
1. A method for analyzing and detecting a synthesized PEEK sample comprises a method for detecting the contents of hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone in a reaction system, and is characterized in that the method comprises the following operation steps:
s11, preparing a high performance liquid chromatograph provided with an ultraviolet detector and a chromatographic column, adjusting the sample injection amount to 5 mu L, setting the mobile phase parameter to be acetonitrile/pure water =65/35 isocratic elution, setting the flow rate to be 1.0mL/min, setting the column temperature to be 30 ℃, and setting the wavelength of the ultraviolet detector to be 235 nm; the chromatographic column is a C18 reverse phase column;
s12, mixing acetonitrile and pure water according to a volume ratio of 65/35 to prepare a mobile phase;
s13, preparing a proper amount of standard substances of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone into standard substance solution samples with different concentrations by using a mobile phase for later use so as to obtain a concentration-absorbance standard curve;
s14, taking the object to be measured with known quality, diluting the object to be measured into a solution sample to be measured by a mobile phase according to a certain dilution multiple, and filtering the solution sample for later use;
s15, setting sequence parameters, carrying out sample injection analysis after the high performance liquid chromatograph is stabilized, sequentially carrying out peak discharge sequence on the solution sample to be detected including hydroquinone, diphenyl sulfone and 4, 4-difluorobenzophenone, and recording each absorption peak by an ultraviolet detector;
and S16, fitting the absorption peak area of the solution sample to be detected and the concentration-absorbance standard curve of the standard solution sample, and respectively calculating the contents of hydroquinone, diphenyl sulfone and 4, 4' -difluorobenzophenone in the substance to be detected by using the peak area and the dilution times.
2. The method according to claim 1, wherein in step S13, the standard solution sample concentration comprises 5mg/L, 50mg/L, 100mg/L, 250mg/L and 500 mg/L.
3. The method as claimed in claim 1, wherein in step S14, 4g ± 0.2g of the specimen is taken, and the specimen is added into a 100mL volumetric flask with mobile phase to prepare a specimen of the solution to be tested, and filtered with an organic filter membrane for use.
4. The method according to claim 1, further comprising a method for detecting the molecular weight of PEEK synthesized in the reaction system, the method comprising the steps of:
s21, preparing a gel permeation chromatograph provided with a differential detector and a gel chromatographic column, setting a quantitative ring at 25 mu L, a sample injection amount at 20-40 mu L, isocratic elution with dichloroacetic acid/dichloromethane = 7/3-9/1 as mobile phase parameters, setting a flow rate at 0.7-1.0 mL/min, a column temperature at 30 ℃, and an analysis time: not less than 30 min;
s22, mixing dichloroacetic acid and dichloromethane according to a volume ratio of 7/3-9/1 to prepare a mobile phase;
s23, respectively dissolving three high molecular polymer standard substances with different weight average molecular weights Mw into a mobile phase to prepare a standard solution sample of 10mg/mL for later use so as to obtain a linear regression equation;
s24, dissolving the product PEEK with known mass in a mobile phase to prepare a solution sample to be detected with the mass fraction of 2 per mill, and filtering for later use; firstly, dissolving a sample into a 1% solution by using dichloroacetic acid at the temperature of 150 ℃, then diluting the sample into a 2 per mill sample solution by using dichloromethane, and filtering the sample by using an organic filter membrane for later use;
s25, after the gel permeation chromatograph is stabilized, the sample of the standard solution is injected and analyzed, the differential chromatogram is recorded, the standard curve is drawn by the special software of GPC, and the linear regression equation is logMw a + bRT;
wherein Mw is the known weight average molecular weight of the standard solution sample, and RT is the retention time of the standard solution sample;
s26, then, carrying out sample injection analysis on the solution sample to be detected, recording a differential chromatogram, and calculating the molecular weight by combining a linear regression equation as follows:
weight average molecular weight Mw = Σ (RIi Mi)/Σ RIi; number average molecular weight Mn = Σ RIi/Σ (RIi/Mi);
dispersion coefficient D = Mw/Mn;
wherein RIi is the peak height of the differential chromatogram of the solution sample to be detected, and Mi is the molecular weight obtained by substituting the i time point on the differential chromatogram of the solution sample to be detected into the standard curve.
5. The method of claim 4, wherein in step S23, M is usedWAnd (4) polystyrene standards of =193000Da, 42600Da and 16200 Da.
6. The method according to claim 4, wherein in step S21, the type of the gel chromatography column is Agilent MIXED-B, 300mm x 7.5mm, 10 μm, and the number of the gel chromatography columns used is 2.
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