Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a detection method of an organic electroluminescent material, which detects a sample to be detected by ultra-high performance liquid chromatography combined with mass spectrometry and selects a phenyl chromatographic column, thereby improving the separation degree of the sample to be detected and realizing qualitative and quantitative detection of the organic electroluminescent material in a short time.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a detection method of an organic electroluminescent material, which comprises the following steps: detecting a sample to be detected by ultra-high performance liquid chromatography combined with mass spectrometry; the chromatographic column of the ultra-high performance liquid chromatography is a phenyl chromatographic column.
The detection method provided by the invention is carried out by adopting ultra-high performance liquid chromatography combined with mass spectrometry and matched with a specific phenyl chromatographic column, is particularly suitable for synthetic products with large molecular weight and high boiling point in organic electroluminescent materials, and has the characteristics of good separation effect, short analysis time and high accuracy.
In the present invention, the packing particle size of the phenyl chromatographic column is 1.6-3 μm, such as 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm or 2.9 μm, and the specific values therebetween are limited to space and for simplicity, and the present invention does not exhaust the specific values included in the range, preferably 1.7-2.5 μm.
As a preferred technical scheme of the invention, the filler particle size of the phenyl chromatographic column is 1.6-3 μm; if the particle size of the filler is beyond the range, the separation time is long and the separation effect is relatively poor due to the overlarge particle size of the filler; too small a filler particle size can cause too much pressure and the detection system cannot bear it.
Preferably, the specification of the phenyl chromatographic column is: 3.0 mm. times.100 mm, 2.5. mu.m.
In the invention, the mobile phase A of the ultra-high performance liquid chromatography comprises an aqueous solution containing 0.1% formic acid.
Preferably, the mobile phase B of the ultra-high performance liquid chromatography comprises an acetonitrile solution containing 0.1% formic acid.
Preferably, the analytical gradient of the ultra-high performance liquid chromatography is as follows: 0-14 min, 50-90% of mobile phase B; 14-17 min, 90% of mobile phase B; 17-20 min, 90-50% of mobile phase B.
Preferably, the analytical gradient of the ultra-high performance liquid chromatography is as follows: 0-12 min, 50-90% of mobile phase B; 12-17 min, 90% of mobile phase B; 17-20 min, 90-50% of mobile phase B.
Preferably, the analytical gradient of the ultra-high performance liquid chromatography is as follows: 0-8 min, 50-90% of mobile phase B; 8-17 min, 90% of mobile phase B; 17-20 min, 90-50% of mobile phase B.
Preferably, the analysis time of the ultra-high performance liquid chromatography is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the detection wavelength of the ultra-high performance liquid chromatography is 254 nm.
Preferably, the flow rate of the phenyl chromatographic column is 0.2-0.6 mL/min, such as 0.25mL/min, 0.3mL/min, 0.35mL/min, 0.4mL/min, 0.45mL/min, 0.5mL/min, or 0.55mL/min, and the specific values therebetween, are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
The detection method provided by the invention has the advantages that through the control and optimization of a specific test system and chromatographic conditions, the analysis time is shortened to be within 30min, the solvent consumed by analyzing one sample is about 10mL, the detection solvent consumption and the waste liquid output are obviously reduced, on one hand, the reagent cost required by detection is reduced, on the other hand, more industrial three wastes are avoided, and the detection method is more environment-friendly.
Preferably, the column temperature of the phenyl chromatography column is 40 ℃.
In the present invention, the concentration of the sample to be tested is 0.5-1.5 mg/mL, such as 0.6mg/mL, 0.7mg/mL, 0.8mg/mL, 0.9mg/mL, 1.0mg/mL, 1.1mg/mL, 1.2mg/mL, 1.3mg/mL or 1.4mg/mL, and the specific values therebetween are not limited to space and for brevity, and the specific values included in the range are not exhaustive.
Preferably, the sample to be detected is a solution of an organic electroluminescent material.
Preferably, the solvent of the solution comprises dichloromethane.
Preferably, the sample to be tested has a sample injection volume of 0.5-1.5 μ L, such as 0.6 μ L, 0.7 μ L, 0.8 μ L, 0.9 μ L, 1.0 μ L, 1.1 μ L, 1.2 μ L, 1.3 μ L or 1.4 μ L, and specific values therebetween, which is not limited by space and for brevity, the present invention is not exhaustive of the specific values included in the range.
In the present invention, the relative molecular mass of the organic electroluminescent material is 200 to 900, such as 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800 or 850, and the specific values therebetween are limited to the space and for the sake of brevity, and the specific values included in the range are not exhaustive.
Preferably, the organic electroluminescent material is an organic compound containing at least one of C6-C30 aryl, C3-C20 heteroaryl or C6-C30 arylamine.
The C6 to C30 aryl groups include aryl groups of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, illustratively including but not limited to phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, or the like.
The heteroaryl group of C3 to C20 includes heteroaryl groups of C6, C9, C10, C12, C14, C16, C18, C20, and the like, and exemplarily includes, but is not limited to, pyridyl, furyl, thienyl, carbazolyl, indolyl, acridinyl, hydrogenated acridinyl, quinolyl, isoquinolyl, phenothiazinyl, phenoxazinyl, and the like.
The C6-C30 arylamine group includes arylamine groups of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc., and exemplarily includes but is not limited to a toluidine group, a dianiline group, a xylidine group, a trianilide group, a naphthylamine group, a benzylamine group, a diphenyl-p-phenylenediamine group or a phenethylamine group, etc.
In the present invention, the ion mode of the mass spectrum is a positive ion mode.
Preferably, the corona needle current of the mass spectrum is 10 μ Α.
Preferably, the cone hole voltage of the mass spectrum is 10 kV;
preferably, the source temperature of the mass spectrum is 120 ℃;
preferably, the desolvation gas temperature of the mass spectrum is 350 ℃;
preferably, the flow speed of the blowback air of the mass spectrum is 50L/min;
preferably, the mass spectrum has a desolventizing gas flow rate of 500L/min.
In the invention, the detection method comprises the following steps: detecting an organic compound containing a sample to be detected by ultra-high performance liquid chromatography-mass spectrometry; the chromatographic column of the ultra-high performance liquid chromatography is a phenyl chromatographic column; the particle size of the filler of the phenyl chromatographic column is 1.6-3 mu m;
the sample to be detected is a solution of an organic electroluminescent material, and the sample injection volume is 0.5-1.5 mu L; the concentration of the solution is 0.5-1.5 mg/mL; the relative molecular mass of the organic electroluminescent material is 200-900, and the organic electroluminescent material is an organic compound containing at least one of C6-C30 aryl, C3-C20 heteroaryl or C6-C30 arylamine;
the chromatographic conditions of the ultra-high performance liquid chromatography comprise: the analysis time is 10-30 min, the detection wavelength is 254nm, the flow rate is 0.2-0.6 mL/min, the column temperature is 40 ℃, the mobile phase A comprises an aqueous solution containing 0.1% formic acid, and the mobile phase B comprises an acetonitrile solution containing 0.1% formic acid;
the conditions of the mass spectrum include: the ion mode is positive ion mode, corona needle current is 10 μ A, taper hole voltage is 10kV, source temperature is 120 deg.C, desolvation gas temperature is 350 deg.C, back blowing gas flow rate is 50L/min, and desolvation gas flow rate is 500L/min.
Compared with the prior art, the invention has the following beneficial effects:
the detection method provided by the invention realizes the detection of the organic electroluminescent material by adopting the ultra-high performance liquid chromatography-mass spectrometry, realizes the effective separation and qualitative and quantitative detection of the sample by the control and optimization of a specific test system, a chromatographic column and chromatographic conditions and the combination of the specific test system, the chromatographic column and the mass spectrometry, shortens the analysis time to be within 30min, has short analysis time, good detection precision and accuracy and less consumption of organic solvent, and effectively solves the defects of high detection cost and large amount of waste liquid caused by purchasing the organic solvent. The detection method has the advantages of high separation degree and high accuracy, is short in detection time, low in cost and more environment-friendly, can particularly realize accurate separation and detection of the organic electroluminescent material containing the triphenylamine group, and has wide application prospect.
Example 2
A detection method of an organic electroluminescent material comprises the following steps:
(1) sample pretreatment: taking a mixture containing 1-bromo-3-fluoro-4-iodobenzene and a target product
Putting 1mg of the mixture into a 2mL automatic sample injector vial, adding 1mL of dichloromethane, ultrasonically dissolving until the mixture is clear and transparent, and taking 1 mu L of the mixture for sample loading test;
(2) and (3) detection process: detecting by ultra performance liquid chromatography-mass spectrometry, wherein the test system is Waters Aqulity H-class (UPLC), the chromatographic column is Phenyl chromatographic column BEH Phenyl with specification of 3.0mm × 100mm and 2.5 μm; the chromatographic conditions were as follows: the detection wavelength is 254nm, the flow rate is 0.5mL/min, the column temperature is 40 ℃, the mobile phase A is an aqueous solution containing 0.1% formic acid, the mobile phase B is an acetonitrile solution containing 0.1% formic acid, and the analytical gradient is as follows: 0-8 min, 50-90% of mobile phase B; 8-17 min, 90% of mobile phase B; 17-20 min, 90-50% of mobile phase B; other conditions and procedures were the same as in example 1;
the chromatogram obtained by the detection method provided in this example is shown in FIG. 4, where 1 represents the peak of 1-bromo-3-fluoro-4-iodobenzene, and 2 represents the target compound
As can be seen from the figure, the separation peak of 1-bromo-3-fluoro-4-iodobenzene appears at a time of 5.8 min; when the time is 6.2min, a separation peak of the target compound appears, which indicates that baseline separation of the 1-bromo-3-fluoro-4-iodobenzene and the target compound is completed at this time, in this example, the chromatographic conditions are further optimized on the basis of example 1, so that baseline separation of two materials is achieved in a shorter time, and the working efficiency is higher.
Comparative example 1
(1) Sample pretreatment: taking the mixture containing 1-bromo-3-fluoro-4-iodobenzene and a target product
1mg of the mixture of (A) and (B) is placed inAdding 1mL of dichloromethane into a 2mL automatic sample injector bottle, ultrasonically dissolving until the solution is clear and transparent, and taking 5 mu L of solution for sample loading test;
(2) and (3) detection process: adopting a High Performance Liquid Chromatograph (HPLC), wherein the test system is Shimadzu LC2030(HPLC), the chromatographic column is Shim pack GIST C18, and the specification is 4.6mm multiplied by 150mm and 5 mu m; the chromatographic conditions were as follows: the detection wavelength is 254nm, the flow rate is 2.0mL/min, the column temperature is 40 ℃, the mobile phase A is an aqueous solution containing 0.1% formic acid, the mobile phase B is an acetonitrile solution containing 0.1% formic acid, and the analytical gradient is as follows: 0-30 min, 50-90% of mobile phase B; 30-50 min, 90% of mobile phase B; 90-50% of mobile phase B in 50-60 min;
the chromatogram obtained by the detection method provided in this comparative example is shown in FIG. 5, in which 1 represents the peak of 1-bromo-3-fluoro-4-iodobenzene, and 2 represents the target compound
The peak of (2) can be seen from the figure, when the time is 19.5min, the peaks of the two materials are still difficult to distinguish, which indicates that the two materials can not be separated; the detection method provided by the
embodiment 1 of the invention can realize the baseline separation of the two materials within 8 min; in addition, in the comparative example, a single needle sample consumes 120mL of solvent, consumes more solvent, has higher cost and causes more waste liquid; in contrast, in the detection method provided by
embodiment 1 of the present invention, the solvent dosage of a single needle sample is only 10mL, so that the detection method provided by the present invention has more excellent separation and detection effects and less organic solvent dosage.
Comparative example 2
A detection method of an organic electroluminescent material comprises the following steps:
(1) sample pretreatment: taking a mixture containing 1-bromo-3-fluoro-4-iodobenzene and a target product
1mg of the mixture (A) was placed in a 2mL autosampler vial, 1mL of dichloromethane was added, the mixture was ultrasonically dissolved until it was clear and transparent, and 1. mu.L of the mixture was sampled:
(2) and (3) detection process: adopting an Ultra Performance Liquid Chromatograph (UPLC), wherein the testing system is Waters Aqulity H-class, the chromatographic column is BEH C18, and the specification is 3.0mm multiplied by 100mm and 2.5 mu m; the chromatographic conditions were as follows: the detection wavelength is 254nm, the flow rate is 0.5mL/min, the column temperature is 40 ℃, the mobile phase A is an aqueous solution containing 0.1% formic acid, the mobile phase B is an acetonitrile solution containing 0.1% formic acid, and the analytical gradient is as follows: 0-12 min, 50-90% of mobile phase B; 12-17 min, 90% of mobile phase B; 17-20 min, 90-50% of mobile phase B;
the chromatogram obtained by the detection method provided by the comparative example is shown in fig. 6, wherein 1 represents the peak of 1-bromo-3-fluoro-4-iodobenzene, and 2 represents the peak of the target compound, and as can be seen from fig. 6, when the retention time is 8.5min, the peaks of the two materials are separated, but do not reach the baseline, so that an accurate analysis result cannot be obtained, which indicates that an ideal detection result cannot be obtained by adopting an ultra-high performance liquid chromatograph in combination with a conventional C18 chromatographic column; the detection method provided by the invention can realize separation of two materials and reach a baseline by ultra-high performance liquid chromatography and matching with a specific phenyl chromatographic column when the retention time is 8min, thereby illustrating the advantages of the detection method provided by the invention.
The applicant states that the present invention is illustrated by the above examples to describe the method for detecting an organic electroluminescent material of the present invention, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.