CN113899838A - Method for detecting purity of benzene ring anhydride compound - Google Patents

Method for detecting purity of benzene ring anhydride compound Download PDF

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CN113899838A
CN113899838A CN202111063320.8A CN202111063320A CN113899838A CN 113899838 A CN113899838 A CN 113899838A CN 202111063320 A CN202111063320 A CN 202111063320A CN 113899838 A CN113899838 A CN 113899838A
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benzene ring
anhydride compound
phase
ring
purity
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CN113899838B (en
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孙长军
薛单单
杨建华
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Quzhou Kangpeng Chemical Co ltd
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Abstract

The invention provides a method for detecting the purity of a benzene ring anhydride compound, which comprises the following steps: adding a derivatization reagent and an organic solvent into a benzene ring anhydride compound sample, heating and cooling to obtain a liquid to be detected, detecting by adopting a liquid chromatography, comparing retention time for qualitative determination, and determining the relative content of the benzene ring anhydride compound and ring-opening impurities in the liquid to be detected by a peak area normalization method so as to determine the purity of the benzene ring anhydride compound. The method for detecting the purity of the benzene ring anhydride compound can realize the complete separation of the benzene ring anhydride compound and related impurities, and has the advantages of good precision and accuracy and accurate result.

Description

Method for detecting purity of benzene ring anhydride compound
Technical Field
The invention belongs to the technical field of organic compound purity detection, and relates to a method for detecting the purity of a benzene ring anhydride compound.
Background
The benzene ring acid anhydride compound can be widely used in fine chemical products, such as: ODPA, chemically known as 4,4' -oxydiphthalic anhydride, is a key intermediate for polymeric materials, and is used in composites, foams, adhesives, molded parts, films, and the like. The polyimide is an important raw material for preparing polyimide, and can be widely used for packaging LED lamps, alignment films of liquid crystal screens and some parts in automobiles. For another example: 6FDA, chemical name of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, is one of six dianhydride monomers which are most widely used, and is also the dianhydride monomer which is used in the largest amount in colorless transparent polyimide at present. The glass transition temperature of the polyimide synthesized by 6FDA is usually 300 ℃ or higher, and the balance between mechanical properties and electrical properties is good, and the fluorine-containing polyimide is still the most representative.
The benzene ring acid anhydride compound is hydrolyzed to cause acid anhydride ring opening, ring opening impurities are generated to influence the cyclization rate of the compound, and the content of the ring opening impurities directly influences the quality of downstream polymerization reaction products, so that the accurate detection of the cyclization rate of the compound has very important significance. Currently, two detection means are commonly used for such compounds: 1. firstly, hydrolyzing a compound with alkali and then carrying out joint measurement by HPLC, and counting the content of impurities into a main component, so that the purity cannot really reflect the quality of the compound. 2. The content of single ring-opening impurities cannot be reflected by adopting a titration method for analysis, and the cyclization rate is inaccurate.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for detecting the purity of benzene ring anhydride compound, which can effectively detect the benzene ring anhydride compound and its ring-opening impurities by using a pre-treatment manner of derivatization, thereby effectively controlling the quality of the purity of the benzene ring anhydride compound.
In order to achieve the above objects and other related objects, the present invention provides a method for detecting purity of benzene ring anhydride compound, comprising: adding a derivatization reagent and an organic solvent into a benzene ring anhydride compound sample, heating and cooling to obtain a liquid to be detected, detecting by adopting a liquid chromatography, comparing retention time for qualitative determination, and determining the relative content of the benzene ring anhydride compound and ring-opening impurities in the liquid to be detected by a peak area normalization method so as to determine the purity of the benzene ring anhydride compound.
Preferably, the derivatizing agent is selected from one of methanol, ethanol, cyclopentylamine or cyclohexylamine.
Preferably, the derivatizing agent is cyclohexylamine.
Preferably, the organic solvent is acetonitrile.
Preferably, the ratio of the mass g of the benzene ring anhydride compound sample to the volume ml of the derivatization reagent is 0.5-1.5: 200.
Preferably, the ratio of the mass g of the benzene ring anhydride compound sample to the volume ml of the derivatization reagent is 1: 200.
Preferably, the ratio of the mass g of the benzene ring anhydride compound sample to the volume ml of the organic solvent is 0.5-1.5: 1000.
Preferably, the ratio of the mass g of the benzene ring anhydride compound sample to the volume ml of the organic solvent is 1: 1000.
Preferably, the heating temperature is 70-90 ℃. Preferably, the temperature of the heating is 80 ℃.
Preferably, the heating time is 2-5 hours. Preferably, the heating time is 3 hours.
Preferably, the heating is performed using an oven.
Preferably, the cooling is to room temperature. The room temperature is 20-30 ℃.
Preferably, the detection by liquid chromatography comprises the following steps:
1) adding water into a benzene ring anhydride compound standard substance and a ring-opening impurity standard substance, then adding a derivatization reagent and an organic solvent, heating and cooling to obtain a positioning solution;
2) mixing a derivatization reagent and an organic solvent, heating and cooling to obtain a blank solution;
3) detecting the liquid to be detected, the positioning solution in the step 1) and the blank solution in the step 2) by adopting a liquid chromatography (HPLC), comparing and retaining time for determining the nature, determining the peak positions of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected, and determining the relative content of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected by a peak area normalization method.
Preferably, in the step 1), the standard substance of the benzene ring anhydride compound is selected from one of 4,4 '-oxydiphthalic anhydride (ODPA), 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3',4,4' -biphenyltetracarboxylic dianhydride.
The CAS number of the above-mentioned 4,4' -oxydiphthalic anhydride (ODPA) is 1823-59-2. The CAS number of the above 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA) is 1107-00-2. The CAS number of the 3,3',4,4' -biphenyltetracarboxylic dianhydride is 2420-87-3.
More preferably, the standard substance of the benzene ring anhydride-based compound is an isomer of a4, 4' -oxydiphthalic anhydride derivative and a4, 4' -oxydiphthalic anhydride derivative contained in 4,4' -oxydiphthalic anhydride (ODPA).
More preferably, the structural formula of the 4,4' -oxydiphthalic anhydride derivative is shown in the specification
Figure BDA0003257421460000021
More preferably, the structural formula of the isomer of the 4,4' -oxydiphthalic anhydride derivative is shown in the specification
Figure BDA0003257421460000031
Preferably, in the step 1), the open-loop impurity standard includes ODPA double-sided open-loop impurity, ODPA single-sided open-loop impurity, and an isomer of ODPA single-sided open-loop impurity.
More preferably, the ODPA double-sided ring-opening impurity is 4, 4-oxydiphthalic acid. The CAS number of the 4, 4-oxydiphthalic acid is 7717-76-2.
More preferably, the ODPA single-side ring-opening impurity has a structural formula of
Figure BDA0003257421460000032
Wherein R is selected from CH3O、C2H5O、
Figure BDA0003257421460000033
One kind of (1). And R is a functional group structure connected after a derivatization reagent reacts.
Further preferably, the ODPA unilateral ring-opening impurity has a structural formula of
Figure BDA0003257421460000034
More preferably, the structural formula of the isomer of ODPA unilateral ring-opening impurity is
Figure BDA0003257421460000035
Wherein R is selected from CH3O、C2H5O、
Figure BDA0003257421460000036
One kind of (1). And R is a functional group structure connected after a derivatization reagent reacts.
Further preferably, the structural formula of the isomer of ODPA unilateral ring-opening impurity is
Figure BDA0003257421460000037
Preferably, in the step 1), the ratio of the mass g of the benzene ring anhydride compound standard substance to the volume ml of water is 0.5-1.5: 100.
preferably, in the step 1), the ratio of the mass g of the benzene ring anhydride compound standard substance to the volume ml of the derivatization reagent is 0.5-1.5:200, and preferably 1: 200.
Preferably, in the step 1), the ratio of the mass g of the benzene ring anhydride compound standard substance to the volume ml of the organic solvent is 0.5-1.5:1000, and preferably 1: 1000.
Preferably, in the step 1), the ratio of the added mass g of the ring-opening impurity standard substance to the added volume ml of water is 0.5-1.5: 100.
preferably, in step 1), the ratio of the mass g of the ring-opened impurity standard substance added to the volume ml of the derivatization reagent added is 0.5-1.5:200, preferably 1: 200.
Preferably, in the step 1), the ratio of the added mass g of the ring-opening impurity standard substance to the added volume ml of the organic solvent is 0.5-1.5:1000, and is preferably 1: 1000.
Preferably, in step 1), the derivatizing agent is selected from one of methanol, ethanol, cyclopentylamine or cyclohexylamine, and is preferably cyclohexylamine.
Preferably, in step 1), the organic solvent is acetonitrile.
In step 2), the above blank solution is used for blank subtraction.
Preferably, in step 2), the ratio of the volume of the derivatization reagent to the volume of the organic solvent added is 150-250: 1000, preferably 200: 1000.
preferably, in step 1) or 2), the temperature of the heating is 70 to 90 ℃. More preferably, the temperature of the heating is 80 ℃.
Preferably, in step 1) or 2), the heating time is 2 to 5 hours. More preferably, the heating time is 3 hours.
Preferably, in step 1) or 2), the heating is performed using an oven.
Preferably, in step 1) or 2), the cooling is to room temperature. The room temperature is 20-30 ℃.
Preferably, in the step 3), the detector used in the liquid chromatography is an ultraviolet detector (UV).
Preferably, in the step 3), the chromatographic column used in the liquid chromatography is an octadecylsilane chemically bonded silica filler chromatographic column, the length of the chromatographic column is 15-25cm, the inner diameter of the chromatographic column is 0.40-0.50mm, and the thickness of the stationary phase membrane is 3.5-5 μm.
More preferably, the chromatographic column used in the liquid chromatography is an Agilent Zorbax XDB-C18 chromatographic column, the length of the chromatographic column is 15cm, the inner diameter is 0.46mm, and the thickness of the stationary phase membrane is 5 μm.
Preferably, in step 3), the column temperature used in the liquid chromatography is 30-40 ℃. More preferably, the column temperature used in the high performance liquid chromatography is 35 ℃.
Preferably, in the step 3), the sample amount used in the liquid chromatography is 5.0 to 20.0. mu.L. More preferably, the amount of sample used in the liquid chromatography is 10.0. mu.L.
Preferably, in step 3), the flow rate used in the liquid chromatography is 0.8-1.2 mL/min. More preferably, the flow rate employed in the liquid chromatography is 1.0 mL/min.
Preferably, in the step 3), the detection wavelength used in the liquid chromatography is 205-215 nm. More preferably, the detection wavelength used in the liquid chromatography is 210 nm.
Preferably, in the step 3), the mobile phase in the liquid chromatography is 0.05-0.2% phosphoric acid water solution-acetonitrile, wherein the phase A is 0.05-0.2% phosphoric acid water solution, and the phase B is acetonitrile; the analysis time is 70 min; gradient elution.
More preferably, in the liquid chromatography, the mobile phase is 0.1% phosphoric acid aqueous solution-acetonitrile, wherein the phase A is 0.1% phosphoric acid aqueous solution, and the phase B is acetonitrile; the analysis time is 70 min; gradient elution.
The 0.05-0.2% phosphoric acid aqueous solution is 0.05-0.2% phosphoric acid aqueous solution by volume percentage. The 0.1% phosphoric acid aqueous solution is 0.1% phosphoric acid aqueous solution in volume percentage.
More preferably, as shown in table 1, the specific procedure of the gradient elution is:
0-5min, phase A: the volume ratio of the phase B is 90: 10-90: 10;
5-30min, phase A: the volume ratio of the phase B is 90: 10-50: 50;
30-40min, phase A: the volume ratio of the phase B is 50: 50-5: 95;
40-50min, phase A: the volume ratio of the phase B is 5: 95-5: 95;
50-55.01min, phase A: the volume ratio of the phase B is 5: 95-90: 10;
55.01-70min, phase A: the volume ratio of the phase B is 90: 10-90: 10.
TABLE 1
Figure BDA0003257421460000051
Preferably, in step 3), the peak area normalization method is: after HPLC detection is carried out on the benzene ring anhydride compound sample, the chromatographic peak areas of the benzene ring anhydride compound and the ring-opening impurities in the liquid to be detected are obtained through calculation, the sum of the areas of the chromatographic peaks after blank solution is deducted from the liquid to be detected is calculated, and the total chromatographic peak area is obtained. And then, dividing the chromatographic peak area of the benzene ring anhydride compound by the total chromatographic peak area to obtain the percentage of the chromatographic peak area of the benzene ring anhydride compound in the total chromatographic peak area, namely the relative content of the benzene ring anhydride compound in the liquid to be detected.
Preferably, in the step 3), the peak area normalization method is calculated according to the formula (1),
the formula (1) is:
Figure BDA0003257421460000061
in the formula, wiThe relative content of the benzene ring anhydride compound in the liquid to be detected; a. theiIs the chromatographic peak area of the benzene ring anhydride compound in the liquid to be detected; sigma AiIs the total chromatographic peak area of the solution to be detected.
The water is pure water.
As described above, the method for detecting the purity of the benzene cyclic anhydride compound provided by the invention can realize complete separation of the benzene cyclic anhydride compound and related impurities, so that the purity of the benzene cyclic anhydride compound can be effectively determined. The method can realize effective separation of the benzene ring anhydride compound and the ring-opening impurities thereof, has good precision and accuracy and accurate result, can accurately reflect the purity and quality of the benzene ring anhydride compound, and has very important significance for monitoring the quality of the benzene ring anhydride compound.
Drawings
FIG. 1 shows a liquid chromatogram of a blank solution for determining ODPA in the present invention.
FIG. 2 shows a liquid chromatogram of a positioning solution for ODPA assay in the present invention, wherein a is the ODPA double side open-ring impurity, b is the ODPA single side open-ring impurity, c is the isomer of the ODPA single side open-ring impurity, d is the ODPA derivative, and e is the isomer of the ODPA derivative.
FIG. 3 shows a liquid chromatogram of a sample for measuring an actual benzene ring anhydride compound in the present invention.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The reagents and equipment used in the following examples are as follows:
1. reagent
4,4' -oxydiphthalic anhydride compound samples (Zhuo 29130, Calif.). 4,4' -oxydiphthalic anhydride standard (purity > 99.8%, echiei (shanghai) chemical industry development limited) in which both the 4,4' -oxydiphthalic anhydride derivative and the isomer of the 4,4' -oxydiphthalic anhydride derivative are present. Open-ring impurity standards (merck, germany), in which ODPA double-sided open-ring impurities, ODPA single-sided open-ring impurities, and isomers of ODPA single-sided open-ring impurities are present at the same time. Methanol, ethanol, cyclopentylamine, cyclohexylamine (purity is more than or equal to 99.9 percent, sigma-aldich company); acetonitrile (chromatographically pure, merck, germany); pure water (manufactured by Millipop water purifier).
2. Instrument for measuring the position of a moving object
Agilent model 1200 liquid chromatograph (Agilent, usa), equipped with an ultraviolet detector; AgilentZorbax XDB-C18 (150X 0.46mm, 5 μm) (Agilent, USA).
Example 1
1. Sample pretreatment
Taking 0.05g of a benzene ring anhydride compound ODPA sample, adding a derivatization reagent: 10ml of cyclohexylamine and organic solvent: and mixing 50ml of acetonitrile, placing the mixture in an oven at 80 ℃ for heating for 3 hours, and cooling to obtain a solution to be detected. Wherein, the ODPA sample concentration in the solution to be detected is 0.05g (namely 50mg)/50 mL-1 mg/mL.
Taking 0.05g of benzene ring anhydride compound standard substance and 0.05g of ring-opening impurity standard substance, adding 5ml of pure water, and then adding a derivatization reagent: 10ml of cyclohexylamine and organic solvent: after mixing acetonitrile 50ml, placing the mixture in an oven at 80 ℃ for heating for 3 hours, and cooling to obtain a positioning solution. The benzene ring acid anhydride compound standard substance is 4,4' -oxydiphthalic anhydride derivative contained in 4,4' -oxydiphthalic anhydride (ODPA) and isomer of 4,4' -oxydiphthalic anhydride derivative.
Taking a derivatization reagent: 10ml of cyclohexylamine and organic solvent: after mixing acetonitrile 50ml, placing the mixture in an oven at 80 ℃ for heating for 3 hours, and cooling to obtain a blank solution.
2. Measurement of
And (3) detecting the liquid to be detected, the positioning solution and the blank solution prepared in the step (1) by adopting HPLC (high performance liquid chromatography), comparing and retaining time according to the measured value of the positioning solution for qualification, determining the peak positions of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected, and determining the relative contents of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected by a peak area normalization method. The liquid chromatogram of the specific measurement result is shown in FIGS. 1, 2, and 3, and the comparison of FIGS. 1, 2, and 3 shows that benzene in the positioning solution and the solution to be measuredThe separation effect of the cyclic acid anhydride compound and the ring-opening impurities is obvious. In fig. 2, a is ODPA double-sided ring-opening impurity: 4, 4-oxydiphthalic acid; b is ODPA single side ring-opening impurity with the structural formula
Figure BDA0003257421460000081
c is an isomer of ODPA unilateral ring-opening impurity with the structural formula
Figure BDA0003257421460000082
d is ODPA derivative with the structural formula
Figure BDA0003257421460000083
e is an isomer of ODPA derivative with the structural formula
Figure BDA0003257421460000084
In specific determination, the detection conditions of the HPLC method are as follows: the detector is an ultraviolet detector (UV); the chromatographic column is an Agilent Zorbax XDB-C18 chromatographic column (150X 0.46mm, 5 μm); the sample injection amount is 10 mu L; the flow rate is 1.0 mL/min; the column temperature was 35 ℃; the detection wavelength is 210 nm; the mobile phase is 0.1% phosphoric acid water solution-acetonitrile, wherein, the phase A is 0.1% phosphoric acid water solution, and the phase B is acetonitrile; the analysis time is 70 min; gradient elution.
The specific procedure for gradient elution is shown in table 1 as:
0-5min, phase A: the volume ratio of the phase B is 90: 10-90: 10;
5-30min, phase A: the volume ratio of the phase B is 90: 10-50: 50;
30-40min, phase A: the volume ratio of the phase B is 50: 50-5: 95;
40-50min, phase A: the volume ratio of the phase B is 5: 95-5: 95;
50-55.01min, phase A: the volume ratio of the phase B is 5: 95-90: 10;
55.01-70min, phase A: the volume ratio of the phase B is 90: 10-90: 10.
the peak area normalization method is as follows: after HPLC detection is carried out on the benzene ring anhydride compound sample, the chromatographic peak areas of the benzene ring anhydride compound and the ring-opening impurities in the liquid to be detected are obtained through calculation, the sum of the areas of all chromatographic peaks in the liquid to be detected is calculated, and the total chromatographic peak area is obtained. And then, dividing the chromatographic peak area of the benzene ring anhydride compound by the total chromatographic peak area to obtain the percentage of the chromatographic peak area of the benzene ring anhydride compound in the total chromatographic peak area, namely the relative content of the benzene ring anhydride compound in the liquid to be detected.
The peak area normalization method is calculated according to the formula (1), wherein the formula (1) is as follows:
Figure BDA0003257421460000085
in the formula, wiThe relative content of the benzene ring anhydride compound in the liquid to be detected; a. theiIs the chromatographic peak area of the benzene ring anhydride compound in the liquid to be detected; sigma AiIs the total chromatographic peak area of the solution to be detected.
Example 2
1. Sample pretreatment
And (3) putting a 60mg benzene ring anhydride compound ODPA sample into a glass bottle with a heating seal, adding 10mL cyclohexylamine and 50mL acetonitrile, heating in an oven at 80 ℃ for 3 hours, and cooling to obtain a solution to be detected.
And (3) putting 60mg of benzene ring anhydride compound standard substance and 60mg of ring-opening impurity standard substance into a heatable sealed glass bottle, adding 5mL of pure water, adding 10mL of cyclohexylamine and 50mL of acetonitrile, heating in an oven at 80 ℃ for 3 hours, and cooling to obtain a positioning solution. The benzene ring acid anhydride compound standard substance is 4,4' -oxydiphthalic anhydride derivative contained in 4,4' -oxydiphthalic anhydride (ODPA) and isomer of 4,4' -oxydiphthalic anhydride derivative.
10mL of cyclohexylamine and 50mL of acetonitrile are added, mixed, placed in an oven at 80 ℃ for heating for 3 hours, and cooled to obtain a blank solution.
2. Measurement of
And (3) detecting the liquid to be detected, the positioning solution and the blank solution prepared in the step (1) by adopting HPLC (high performance liquid chromatography), comparing and retaining time according to the measured value of the positioning solution for qualification, determining the peak positions of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected, and determining the relative contents of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected by a peak area normalization method. The liquid chromatogram of the specific measurement result is shown in fig. 1, 2 and 3, and the comparison of fig. 1, 2 and 3 shows that the method has a very good separation effect on the ring-opening impurities from the phthalic anhydride compounds.
In specific determination, the detection conditions of the HPLC method are as follows: the detector is an ultraviolet detector (UV); the chromatographic column is an Agilent Zorbax XDB-C18 chromatographic column (150X 0.46mm, 5 μm); the sample injection amount is 10 mu L; the flow rate is 1.0 mL/min; the column temperature was 35 ℃; the detection wavelength is 210 nm; the mobile phase is 0.1% phosphoric acid water solution-acetonitrile, wherein, the phase A is 0.1% phosphoric acid water solution, and the phase B is acetonitrile; the analysis time is 70 min; gradient elution.
The specific procedure for gradient elution is shown in table 1 as:
0-5min, phase A: the volume ratio of the phase B is 90: 10-90: 10;
5-30min, phase A: the volume ratio of the phase B is 90: 10-50: 50;
30-40min, phase A: the volume ratio of the phase B is 50: 50-5: 95;
40-50min, phase A: the volume ratio of the phase B is 5: 95-5: 95;
50-55.01min, phase A: the volume ratio of the phase B is 5: 95-90: 10;
55.01-70min, phase A: the volume ratio of the phase B is 90: 10-90: 10.
the peak area normalization method is as follows: after HPLC detection is carried out on the benzene ring anhydride compound sample, the chromatographic peak areas of the benzene ring anhydride compound and the ring-opening impurities in the liquid to be detected are obtained through calculation, the sum of the areas of all chromatographic peaks in the liquid to be detected is calculated, and the total chromatographic peak area is obtained. And then, dividing the chromatographic peak area of the benzene ring anhydride compound by the total chromatographic peak area to obtain the percentage of the chromatographic peak area of the benzene ring anhydride compound in the total chromatographic peak area, namely the relative content of the benzene ring anhydride compound in the liquid to be detected.
The peak area normalization method is calculated according to the formula (1), wherein the formula (1) is as follows:
Figure BDA0003257421460000091
in the formula, wiIs a benzene ring anhydride compound in the liquid to be detectedRelative amounts of (A) and (B); a. theiIs the chromatographic peak area of the benzene ring anhydride compound in the liquid to be detected; sigma AiIs the total chromatographic peak area of the solution to be detected.
Example 3
Taking 3 kinds of phthalic anhydride compound ODPA samples produced by different manufacturers respectively, wherein the serial numbers are 1#, 2#, and 3#, preparing a solution to be detected, a positioning solution, and a blank solution according to the step 1 in the embodiment 2, measuring according to the step 2 in the embodiment 2, and respectively calculating the relative content of ODPA in the solution to be detected through the formula (1). Each identical sample was tested in 5 replicates and the results are shown in tables 2 and 3. As can be seen from tables 2 and 3, the relative content of ODPA measured by the method is RSD less than 0.2%, and the ring-opening impurities of ODPA are measured: the RSD of the relative content measurement result of the ODPA unilateral ring-opening impurity derivative is less than 0.1 percent, and the method has high precision and good reproducibility.
Table 2 results of precision in determining the relative ODPA content for the samples (n ═ 5)
Figure BDA0003257421460000101
Table 3 precision results of the measurement of the relative content of the ring-opening impurities of ODPA (n ═ 5)
Figure BDA0003257421460000102
Example 4
Taking a4, 4' -oxydiphthalic anhydride standard substance (with the purity of more than 99.8%) as a sample, preparing a solution to be detected, a positioning solution and a blank solution according to the step 1 in the example 2, measuring according to the step 2 in the example 2, comparing the measured value with the standard substance identification value, and respectively calculating the relative content of ODPA in the solution to be detected by the formula (1). The results of the 5-time parallel measurement are shown in Table 4. As can be seen from Table 4, the relative content of ODPA measured by the method is RSD less than 0.05%, and the accuracy of the measurement result is high.
Table 4 method accuracy test result confirmation data
Figure BDA0003257421460000111
Example 5
The ODPA sample numbered 2# in example 3 is taken, the test sample is prepared according to the step 1 and the positioning solution is prepared according to the step 2 in example 2, and when the solution to be tested is detected by HPLC, the mobile phases with different proportions are adopted for isocratic elution respectively, and the measurement results are shown in Table 5.
TABLE 5 measurement results of different eluent ratios
Figure BDA0003257421460000112
As can be seen from Table 5, combining the degrees of separation of the main peak from the adjacent impurity components, the peak shapes, and the impurity elution, etc., when the present invention is applied to step 2 in example 2, the main peak can be effectively separated from the adjacent impurities by gradient elution under the preferred conditions.
In conclusion, the invention provides the method for detecting the purity of the benzene ring anhydride compound, which can realize the complete separation of the benzene ring anhydride compound and related ring-opening impurities, and has the advantages of good method precision, accurate result, simple quantitative method and good repeatability. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. A method for detecting the purity of a benzene ring anhydride compound comprises the following steps: adding a derivatization reagent and an organic solvent into a benzene ring anhydride compound sample, heating and cooling to obtain a liquid to be detected, detecting by adopting a liquid chromatography, comparing retention time for qualitative determination, and determining the relative content of the benzene ring anhydride compound and ring-opening impurities in the liquid to be detected by a peak area normalization method so as to determine the purity of the benzene ring anhydride compound.
2. The method for detecting the purity of the benzene ring anhydride compound according to claim 1, characterized by comprising any one or more of the following conditions:
A1) the derivatization reagent is selected from one of methanol, ethanol, cyclopentylamine or cyclohexylamine;
A2) the organic solvent is acetonitrile;
A3) the ratio of the mass of the benzene ring anhydride compound sample to the volume of the derivatization reagent is 0.5-1.5:200 g/ml;
A4) the ratio of the mass of the benzene ring anhydride compound sample to the volume of the organic solvent is 0.5-1.5:1000, g/ml;
A5) the heating temperature is 70-90 ℃;
A6) the heating time is 2-5 hours.
3. The method for detecting the purity of the benzene ring anhydride compound according to claim 1, wherein the detection by liquid chromatography comprises the following steps:
1) adding water into a benzene ring anhydride compound standard substance and a ring-opening impurity standard substance, then adding a derivatization reagent and an organic solvent, heating and cooling to obtain a positioning solution;
2) mixing a derivatization reagent and an organic solvent, heating and cooling to obtain a blank solution;
3) detecting the liquid to be detected, the positioning solution in the step 1) and the blank solution in the step 2) by adopting a liquid chromatography, comparing the retention time, determining the peak positions of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected, and determining the relative content of the benzene ring anhydride compounds and the ring-opening impurities in the liquid to be detected by a peak area normalization method.
4. The method for detecting the purity of the benzene cyclic anhydride compound according to claim 3, wherein in the step 1), the standard product of the benzene cyclic anhydride compound is selected from one of 4,4 '-oxydiphthalic anhydride, 4,4' - (hexafluoroisopropylidene) diphthalic anhydride or 3,3',4,4' -biphenyltetracarboxylic dianhydride; preferably, the standard substance of the benzene ring acid anhydride compound is 4,4' -oxydiphthalic anhydride derivative contained in 4,4' -oxydiphthalic anhydride and an isomer of the 4,4' -oxydiphthalic anhydride derivative.
5. The method for detecting the purity of the benzene ring anhydride compound according to claim 3, wherein in the step 1), the ring-opening impurity standard comprises ODPA double-side ring-opening impurity, ODPA single-side ring-opening impurity and an isomer of ODPA single-side ring-opening impurity; preferably, the ODPA bilateral ring-opening impurity is 4, 4-oxydiphthalic acid; the structural formula of the ODPA unilateral ring-opening impurity is shown in the specification
Figure FDA0003257421450000021
Wherein R is selected from CH3O、C2H5O、
Figure FDA0003257421450000022
One of (1); the structural formula of the isomer of ODPA unilateral ring-opening impurity is shown in the specification
Figure FDA0003257421450000023
Wherein R is selected from CH3O、C2H5O、
Figure FDA0003257421450000024
One kind of (1).
6. The method for detecting the purity of the benzene ring anhydride compound according to claim 3, wherein the step 1) or 2) comprises any one or more of the following conditions:
B1) in the step 1), the ratio of the mass of the benzene ring anhydride compound standard substance to the volume of water is 0.5-1.5:100 g/ml;
B2) in the step 1), the ratio of the mass of the standard substance of the benzene ring anhydride compound to the volume of the derivatization reagent is 0.5-1.5:200 g/ml;
B3) in the step 1), the ratio of the mass of the benzene ring anhydride compound standard substance to the volume of the organic solvent is 0.5-1.5:1000, g/ml;
B4) in the step 1), the ratio of the added mass of the ring-opening impurity standard substance to the added volume of water is 0.5-1.5:100 g/ml;
B5) in the step 1), the ratio of the added mass of the ring-opening impurity standard substance to the added volume of the derivatization reagent is 0.5-1.5:200 g/ml;
B6) in the step 1), the ratio of the added mass of the ring-opening impurity standard substance to the added volume of the organic solvent is 0.5-1.5:1000, g/ml;
B7) in the step 2), the volume ratio of the derivatization reagent to the organic solvent is 150-250: 1000, parts by weight;
B8) in the step 1) or 2), the heating temperature is 70-90 ℃;
B9) in step 1) or 2), the heating time is 2-5 hours.
7. The method for detecting the purity of the benzene ring anhydride compound according to claim 3, wherein in the step 3), the liquid chromatography comprises the following detection conditions: the detector is an ultraviolet detector UV; the chromatographic column adopts octadecylsilane chemically bonded silica filler, the length of the chromatographic column is 15-25cm, the inner diameter is 0.40-0.50mm, and the thickness of the stationary phase membrane is 3.5-5 μm; the detection wavelength is 205-215 nm; the mobile phase is 0.05-0.2% phosphoric acid water solution-acetonitrile, wherein, the phase A is 0.05-0.2% phosphoric acid water solution, and the phase B is acetonitrile; the analysis time is 70 min; gradient elution.
8. The method for detecting the purity of the benzene ring anhydride compound according to claim 7, wherein the specific procedure of the gradient elution is as follows: 0-5min, phase A: the volume ratio of the phase B is 90: 10-90: 10; 5-30min, phase A: the volume ratio of the phase B is 90: 10-50: 50; 30-40min, phase A: the volume ratio of the phase B is 50: 50-5: 95; 40-50min, phase A: the volume ratio of the phase B is 5: 95-5: 95; 50-55.01min, phase A: the volume ratio of the phase B is 5: 95-90: 10; 55.01-70min, phase A: the volume ratio of the phase B is 90: 10-90: 10.
9. the method for detecting the purity of the benzene ring anhydride compound according to claim 3, wherein in the step 3), the liquid chromatography further comprises the following detection conditions: the column temperature is 30-40 ℃; the sample injection amount is 5.0-20.0 muL; the flow rate is 0.8-1.2 mL/min.
10. The method for detecting the purity of the benzene ring anhydride compound according to claim 3, wherein in the step 3), the peak area normalization method is calculated according to a formula (1), and the formula (1) is as follows:
Figure FDA0003257421450000031
in the formula, wiThe relative content of the benzene ring anhydride compound in the liquid to be detected; a. theiIs the chromatographic peak area of the benzene ring anhydride compound in the liquid to be detected; sigma AiIs the total chromatographic peak area of the solution to be detected.
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