CN117776859A - Preparation, separation and purification method of decabromodiphenyl ethane debromination product - Google Patents
Preparation, separation and purification method of decabromodiphenyl ethane debromination product Download PDFInfo
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- CN117776859A CN117776859A CN202410206083.3A CN202410206083A CN117776859A CN 117776859 A CN117776859 A CN 117776859A CN 202410206083 A CN202410206083 A CN 202410206083A CN 117776859 A CN117776859 A CN 117776859A
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- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
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- 238000000746 purification Methods 0.000 title claims abstract description 18
- 238000001782 photodegradation Methods 0.000 claims abstract description 29
- WKVFJZUINSQNRD-UHFFFAOYSA-N BrC1C(C(C(C=C1)(C(C)C1=CC=CC=C1)Br)(Br)Br)(Br)Br Chemical compound BrC1C(C(C(C=C1)(C(C)C1=CC=CC=C1)Br)(Br)Br)(Br)Br WKVFJZUINSQNRD-UHFFFAOYSA-N 0.000 claims abstract description 13
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method, a separation and purification method of a decabromodiphenyl ethane debromination product, and relates to the technical field of compound separation and purification. The method sequentially comprises the steps of preparing a decabromodiphenyl ethane photodegradation sample; detection, separation, preparation, weighing and purity measurement of the debrominated conversion product. The method is based on a decabromodiphenyl ethane photodegradation experiment, and aims at the characteristic of weak polarity of a debrominated degradation product, adopts a high performance liquid chromatography-atmospheric pressure photoionization-time-of-flight mass spectrometry (HPLC-APPI-TOF/MS) combined semi-preparative liquid chromatography (SP-HPLC) technology for the first time, and prepares 2 octabromodiphenyl ethane isomers, 1 heptabromodiphenyl ethane and 1 hexabromodiphenyl ethane with higher purity through mass spectrometry analysis and separation condition optimization of the decabromodiphenyl ethane debrominated compound.
Description
Technical Field
The invention relates to the technical field of compound separation and purification, in particular to a method for preparing, separating and purifying decabromodiphenyl ethane debromination products.
Background
Decabromodiphenyl ethane (decabromodiphenyl ethane, DBDPE) belongs to one of novel brominated flame retardants, and is widely applied to products such as electronic appliances, building material families, plastic textiles and the like because of the advantages of good thermal stability, strong ultraviolet resistance, low leaching rate and the like. DBDPE belongs to an additive type flame retardant, is easy to overflow in the use process of products, and is detected in various environments and biological samples such as sediment, soil, animals and plants and the like at present. Research shows that DBDPE has durability, bioaccumulation, toxicity and long-distance migration capability, and the problem of environmental pollution is highly paid attention to. In addition, two benzene rings of DBDPE are connected through a carbon chain, and have a space cyclic molecular structure, so that DBDPE can be debrominated and hydrogenated to form low-bromine homologs (BDPEs) which are most common in the environment under the actions of ambient light, heat and in-vivo metabolism. The debrominated product is smaller in molecular volume and more readily absorbed by the organism, resulting in greater potential toxicity compared to DBDPE. However, due to the lack of related standards, the debrominated product research reported in the prior art stays in the identification and identification stage, and cannot truly perform structural confirmation, so that the exploration of pollution characteristics, sources and potential toxic effects is limited. Therefore, the preparation of the standard substance of the debrominated product has important significance for exploring the characteristics and the formation mechanism of the debrominated conversion product of DBDPE and developing related bioaccumulation and toxicology evaluation processes.
There are few reports on methods for simultaneously preparing a plurality of DBDPE debrominated conversion products, and the only reports are based on the synthesis of a single compound. CN 102153440a discloses a method for synthesizing octabromodiphenyl ethane, which comprises mixing concentrated sulfuric acid, diphenyl ethane, catalyst, liquid bromine and metal ion remover in turn, wet pulverizing and air flow pulverizing to obtain octabromodiphenyl ethane powder. The method is complex and tedious, more chemicals are used, the raw material cost is high, concentrated sulfuric acid and liquid bromine belong to chemicals easy to prepare, and the experimental danger coefficient is large. CN 101747910a discloses a method for preparing bromodiphenyl ethane, adding brominating agent solution into diphenyl ethane solution added with metal salt lewis acid catalyst, controlling temperature to react at-20-50 ℃ to generate various bromodiphenyl ethane substances, but the bromodiphenyl ethane prepared by the method is a mixture of hexabromodiphenyl ethane and odd bromodiphenyl ethane, and does not generate single bromodiphenyl ethane substance. The prior art shows that the direct synthesis method has the fundamental problem that DBDPE debrominated products cannot be prepared in batches, and the method has the disadvantages of large dosage of dangerous reagents and environment friendliness.
It follows that there is a need for further improvements in the art.
Disclosure of Invention
The invention aims to provide a preparation, separation and purification method of decabromodiphenyl ethane debromination products, by which 2 octabromodiphenyl ethane isomers, 1 heptabromodiphenyl ethane and 1 hexabromodiphenyl ethane can be obtained simultaneously.
In order to achieve the above purpose, the present invention adopts the following technical scheme: preparation, separation and purification method of decabromodiphenyl ethane debromination productThe method sequentially comprises the following steps: step one, preparing a DBDPE standard solution; step two, DBDPE photodegradation: taking 400 mu L of DBDPE standard solution in a quartz glass bottle, using high-pressure mercury lamp ultraviolet light to irradiate and degrade the DBDPE standard solution, passing through a 0.45 mu m organic filter membrane to obtain degraded solution, and transferring the degraded solution into a brown sample bottle to be detected; step three, detecting a debromination product: detecting DBDPE photodegradation product by adopting high performance liquid chromatography-mass spectrometer and based on [ M-Br+O ] in negative ion mode]Identifying DBDPE debromination products by characteristic ion peaks; and step four, separating and preparing a debromination product: separating and collecting photodegradation samples containing DBDPE debromination products by adopting semi-preparative liquid chromatography; the semi-preparative liquid chromatography adopts Agilent Zorbax Eclipse PAH chromatographic column with the specification of 250 mm length, 4.6 mm diameter and 5 μm filler particles; methanol is used as a mobile phase, and the flow rate is 0.8 mL/min; the temperature of the chromatographic column is 30 ℃, 200 mu L of sample is injected each time, and the ultraviolet detection wavelength is 230 nm; step five, weighing: the solution separated and collected in the fourth step is subjected to rotary concentration, and is dried by nitrogen, and then is weighed to obtain four low-bromine diphenyl ethane; step six, purity measurement of the separated product: respectively dissolving four low-bromine diphenylethanes obtained in the fifth step in methanol, and detecting the purity of the four low-bromine diphenylethanes by using a high performance liquid chromatography mass spectrometer to obtain 2 octabromodiphenylethanes (C) 14 H 6 Br 8 ) The purity of the isomers was 82.38% and 88.76%, respectively, and that of heptabromodiphenylethane (C) 14 H 7 Br 7 ) Purity of 97.83%, hexabromodiphenylethane (C) 14 H 8 Br 6 ) The purity was 92.19%.
In the preparation, separation and purification method of the decabromodiphenyl ethane debrominated product, the specific steps for preparing the DBDPE standard solution are as follows: and (3) placing the DBDPE standard substance with the mass fraction of 96% in toluene solution, completely dissolving the DBDPE standard substance through ultrasonic treatment, drying by nitrogen, and switching into methanol solution with the same amount as the toluene solution.
In the preparation, separation and purification method of decabromodiphenyl ethane debromination product, in the second step, the high-pressure mercury lamp is 150W, the horizontal distance between the quartz glass bottle containing the standard solution and the high-pressure mercury lamp is 10 cm, the vertical distance is 15 cm, and the illumination time of the high-pressure mercury lamp is 5 min.
In the third step, the high performance liquid chromatography-atmospheric pressure photoionization-time-of-flight mass spectrometry is adopted by a Agilent Eclipse XDB-C18 chromatographic column with the specification of 150 mm long, the diameter of 2.1 mm, 3.5 μm filler particles and methanol as a mobile phase, the flow rate of the methanol is 0.3 mL/min, the column temperature of the chromatographic column is kept at 23+/-2 ℃ and 2 mu L of the methanol is injected each time.
The preparation, separation and purification method of the decabromodiphenyl ethane debrominated product has the concentration of the DBDPE standard solution of 25 ppm, the ultrasonic power of 500W and the treatment time of 20 min.
The preparation, separation and purification method of the decabromodiphenyl ethane debrominated product are characterized in that toluene and methanol are chromatographic grade.
The preparation, separation and purification method of the decabromodiphenyl ethane debrominated product comprises the steps of quantitatively calculating the purity of four low-bromine diphenyl ethane through peak area.
Compared with the prior art, the invention has the following beneficial technical effects.
(1) Is convenient and quick. The invention has simple operation and short separation period. Traditional synthesis preparation operation is complicated, and the mixture is difficult to separate; the method adopts semi-preparative chromatography to separate and purify various conversion products, and the whole separation process is completed within 60 min, so that various monomers can be obtained by only one step.
(2) The repetition is controllable. The traditional synthesis method has poor controllability and repeatability, and the method has controllable parameters and good repeatability, is suitable for automatic production, and can be popularized and applied.
(3) Is environment-friendly. The invention does not involve dangerous reagent, uses little solvent, and is environment-friendly.
(4) Has great significance. The invention breaks through the bottleneck of DBDPE related conversion product deletion, and provides scientific and effective technical support for separating and purifying DBDPE debrominated products.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a process flow diagram for identification and isolation preparation of DBDPE photodegradation products octabromo, heptabromo and hexabromodiphenylethane.
FIG. 2 (a) is a liquid chromatogram of DBDPE high pressure mercury lamp photodegradation for 5 min; (b) is a mass spectrum of the DBDPE high-pressure mercury lamp photodegradation for 5 min.
FIG. 3 is a separation chromatogram of the DBDPE debrominated conversion products by SP-HPLC different columns.
FIG. 4 is a chromatogram of hexabromodiphenylethane.
Fig. 5 is a mass spectrum of hexabromodiphenylethane.
FIG. 6 is a chromatogram of octabromodiphenylethane.
Fig. 7 is a mass spectrum of octabromodiphenylethane.
FIG. 8 is a chromatogram of heptabromodiphenylethane.
Fig. 9 is a mass spectrum of heptabromodiphenylethane.
FIG. 10 is a chromatogram of octabromodiphenylethane isomers.
FIG. 11 is a mass spectrum of octabromodiphenylethane isomer.
FIG. 12 is a schematic representation of the chemical structural formulas of the prototype compound DBDPE and its photodegradation debrominated conversion products octabromo, heptabromo and hexabromodiphenylethane.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application.
The DBDPE referred to herein is decabromodiphenylethane; the HPLC-APPI-TOF/MS described herein is high performance liquid chromatography-atmospheric pressure photoionization-time of flight mass spectrometry; the SP-HPLC described herein is semi-preparative liquid chromatography.
The technical concept of the invention is that 2 octabromodiphenyl ethane (isomer), 1 heptabromodiphenyl ethane and 1 hexabromodiphenyl ethane are prepared by adopting photocatalysis to degrade decabromodiphenyl ethane and adopting high performance liquid chromatography-atmospheric pressure photoionization-flight time mass spectrum combined semi-preparation liquid chromatography technology to optimize and examine the analysis and separation conditions of DBDPE debrominated compounds.
The chemical structural formulas of the prototype compound DBDPE and the photodegradation debrominated conversion products of octabromo, heptabromo and hexabromodiphenyl ethane are shown in figure 12.
The invention discloses a preparation, separation and purification method of decabromodiphenyl ethane debromination product, which is shown in figure 1, and specifically comprises the following steps: step one, preparing a DBDPE standard solution: putting the DBDPE standard substance with the mass fraction of 96% into toluene solution, and carrying out ultrasonic treatment to completely dissolve the DBDPE standard substance; blowing with nitrogen, and switching to an equivalent methanol solution.
Step two, DBDPE photodegradation: the DBDPE standard solution is degraded by ultraviolet irradiation of a high-pressure mercury lamp, the horizontal distance between a sample and the high-pressure mercury lamp is 10 cm, the vertical distance between the sample and the high-pressure mercury lamp is 15 cm, the sample is subjected to degradation through an organic filter membrane with the thickness of 0.45 mu m to obtain a degradation solution, and the degradation solution is transferred into a brown sample bottle to be detected; the high-pressure mercury lamp is 150-W, and the illumination time is 1-5 min.
Step three, detecting a debromination product: DBDPE photodegradation products were detected by HPLC-APPI-TOF/MS.
HPLC-APPI-TOF/MS adopts Agilent Eclipse XDB-C18 chromatographic column with specification of 150-mm long, diameter of 2.1-mm and filler particle of 3.5 μm; methanol is used as a mobile phase, the flow rate is 0.3 mL/min, the column temperature of the chromatographic column is kept at 23+/-2 ℃, and 2 mu L of the chromatographic column is injected each time. And identifying the debrominated product based on the [ M-Br+O ] characteristic ion peak in the negative ion mode.
And step four, separating and preparing a debromination product: photodegradation samples containing DBDPE debrominated product were collected by separation using SP-HPLC. The concentration of the DBDPE photodegradation sample was 40 ppm. And (3) collecting 8 peaks according to the mass spectrum characteristics in the step (III), placing a collecting bottle corresponding to the 8 peaks in an automatic fraction collecting chamber, setting collecting start and end time nodes, and starting collecting after each sample injection.
Further, SP-HPLC was performed using columns of Agilent ZORBAX CN (4.6X105 mm,5 μm), agilent Zorbax Eclipse PAH (4.6X1250 mm,5 μm), agilent 5 TC-C18 (2) (4.6X150 mm,5 μm) and Kromasil 100-5C18 (4.6X1250 mm,5 μm), respectively; the mobile phase is an organic solvent or an aqueous solution of an organic solvent, including but not limited to methanol, acetonitrile, etc.; ultraviolet detection wavelength 230 nm.
Step five, weighing: concentrating the solution separated and collected in the step four through vacuum rotary evaporation, drying the mobile phase solution through nitrogen to obtain a conversion product, and weighing the mass of the conversion product through a micro-electronic balance in parts per million.
The vacuum rotary evaporation concentration comprises the following steps: the solution from step four was transferred to 8 pear-shaped flasks, respectively, and concentrated to 1 mL by rotary evaporation at 40 ℃. Preparing 8 clean constant-weight sample bottles, respectively transferring 1 mL solution in the pear-shaped bottles into corresponding sample bottles, blow-drying under a mild nitrogen flow, oven-drying to constant weight, weighing, and calculating the quality of the debrominated conversion product collected in the sample bottles by a difference method.
Step six, purity measurement of the separated product: and respectively redissolving the debrominated conversion products in methanol solution, and detecting the purity of the debrominated conversion products by using a high performance liquid chromatography time-of-flight mass spectrometer.
Methanol is of chromatographic purity grade, 3 mL methanol is added to the collected standard substance for dissolution, then the purity is detected by HPLC-APPI-TOF/MS, and the instrument conditions are consistent with those in the third step.
Further description will be provided below with reference to specific examples.
Example 1: the preparation, separation and purification method of decabromodiphenyl ethane debromination product comprises the following steps: (1) preparing DBDPE standard solution: the DBDPE standard with the mass fraction of 96% is dissolved in chromatographic pure toluene to prepare 25 ppm standard solution, and the standard solution is treated by ultrasonic treatment for 20 min to be completely dissolved. Blow-drying with nitrogen, and switching to an equivalent amount of chromatographic pure methanol solution.
(2) DBDPE photodegradation: 400. Mu.L of DBDPE standard solution was taken and irradiated with 150W high pressure mercury lamp ultraviolet light in a 1.5 mL quartz glass bottle for 5 min, the horizontal distance of the quartz glass bottle containing the standard solution and the high pressure mercury lamp was 10 cm, and the vertical distance was 15 cm. The irradiated standard solution is filtered by an organic filter membrane with the thickness of 0.45 mu m to obtain degradation solution, and the degradation solution is transferred into a brown sample bottle to be detected; as shown in fig. 2, fig. 2 (a) shows a liquid chromatogram of degradation of the DBDPE high-pressure mercury lamp for 5 min, and fig. 2 (b) shows a mass chromatogram of degradation of the DBDPE high-pressure mercury lamp for 5 min.
(3) Stripping offQualitative detection of bromine products: detecting the DBDPE photodegradation product by HPLC-APPI-TOF/MS, adopting Agilent Eclipse XDB-C18 chromatographic column with specification of 150-mm long, diameter of 2.1-mm and filler particle of 3.5 μm; an Agilent XDB-C18 guard column (diameter 2.1 mm X column length 12.5 mm, packing particles 5 μm) was provided; methanol is a mobile phase, and the flow rate is 0.3 mL/min; the column temperature of the chromatographic column is kept at 23+/-2 ℃; the sample injection volume is 2 mu L; in APPI - Based on [ M-Br+O ] in mode]And carrying out full scanning (scan) analysis on the characteristic ion peaks, wherein the scanning range m/z is 100-1000.
(4) And (3) separating and preparing a debrominated product: concentrating 25 ppm of DBDPE methanol standard solution to 40 ppm, separating and collecting DBDPE photodegradation sample by SP-HPLC, and adopting Agilent Zorbax Eclipse PAH chromatographic column with specification of 250 mm length, diameter of 4.6 mm and filler particle of 5 μm; methanol is used as a mobile phase, and the flow rate is 0.8 mL/min; column temperature of the chromatographic column is 30 ℃; 200 μl of sample was introduced, and the ultraviolet detection wavelength was 230 nm. According to the mass spectrum characteristics in the step (3), a collection bottle corresponding to 8 peaks is placed in an automatic fraction collection chamber, collection starting and ending time nodes are set, and collection is started after each sample injection.
(5) Weighing: the solutions collected in step (4) were transferred to 8 pear-shaped flasks, respectively, and concentrated to 1 mL by rotary evaporation at 40 ℃ under vacuum. Preparing 8 clean constant-weight sample bottles, transferring 1 mL solution in the pear-shaped bottles to the 8 sample bottles respectively, drying the mobile phase solution under a mild nitrogen flow, drying to constant weight by an oven, weighing, and calculating the mass of the debrominated conversion product collected in the sample bottles by a subtraction method.
(6) Determination of purity of isolated product: and (3) respectively redissolving the dried debrominated conversion products in the step (5) into 3 mL chromatographic pure methanol, detecting the purity of the debrominated conversion products by HPLC-APPI-TOF/MS, and keeping the instrument conditions consistent with those in the step (3). The purity of each substance was quantitatively calculated by peak area. Four of the 8 peaks finally collected were higher in purity, 2 octabromodiphenylethane (C 14 H 6 Br 8 ) The purity of (C) was 82.38% and 88.76%, respectively, heptabromodiphenylethane (C) 14 H 7 Br 7 ) Purity of 97.83%, hexabromodiphenylethane (C) 14 H 8 Br 6 ) The purity was 92.19%. The remaining four substances are basically mixtures of isomers or mixtures of two substances.
Fig. 4 to 11 are respectively a chromatogram and a mass spectrum of hexabromodiphenylethane having high purity, a chromatogram and a mass spectrum of octabromodiphenylethane, a chromatogram and a mass spectrum of heptabromodiphenylethane, and a chromatogram and a mass spectrum of octabromodiphenylethane isomers.
Example 2: the preparation, separation and purification method of decabromodiphenyl ethane debromination product comprises the following steps: (1) preparing DBDPE standard solution: the DBDPE standard with the mass fraction of 96% is dissolved in chromatographic pure toluene to prepare 25 ppm standard solution, and the standard solution is treated by ultrasonic treatment for 20 min to be completely dissolved. Blow-drying with nitrogen, and switching to an equivalent amount of chromatographic pure methanol solution.
(2) DBDPE photodegradation: 400. Mu.L of DBDPE standard solution was taken and irradiated with 150W high-pressure mercury lamp ultraviolet light in a 1.5 mL quartz glass bottle for 5 minutes, the horizontal distance between the quartz glass bottle containing the standard solution and the high-pressure mercury lamp was 10 cm, and the vertical distance was 15 cm. The irradiated standard solution is filtered by an organic filter membrane with the thickness of 0.45 mu m to obtain degradation solution, and the degradation solution is transferred into a brown sample bottle to be detected.
(3) Qualitative detection of debromination products: detecting the DBDPE photodegradation product by HPLC-APPI-TOF/MS, adopting Agilent Eclipse XDB-C18 chromatographic column with specification of 150-mm long, diameter of 2.1-mm and filler particle of 3.5 μm; an Agilent XDB-C18 guard column (diameter 2.1 mm X column length 12.5 mm, packing particles 5 μm) was provided; methanol is a mobile phase, and the flow rate is 0.3 mL/min; the column temperature of the chromatographic column is kept at 23+/-2 ℃; the sample injection volume is 2 mu L; in APPI - Based on [ M-Br+O ] in mode]And carrying out full scanning (scan) analysis on the characteristic ion peaks, wherein the scanning range m/z is 100-1000.
(4) And (3) separating and preparing a debrominated product: concentrating 25 ppm of DBDPE methanol standard solution to 40 ppm, separating and collecting DBDPE photodegradation sample by SP-HPLC, and adopting Agilent ZORBAX CN chromatographic column with specification of 150 mm long, diameter of 4.6 mm and filler particle of 5 μm; the mobile phase is methanol: water = 90:10; column temperature of the chromatographic column is 30 ℃; ultraviolet detection wavelength 230 nm.
Results: in a Agilent ZORBAX CN (4.6X105 mm,5 μm) column, the mobile phase was methanol: water = 90: under 10 conditions, SP-HPLC did not separate the respective peaks corresponding to DBDPE degradation products well.
Example 3: the preparation, separation and purification method of decabromodiphenyl ethane debromination product comprises the following steps: (1) preparing DBDPE standard solution: the DBDPE standard with the mass fraction of 96% is dissolved in chromatographic pure toluene to prepare 25 ppm standard solution, and the standard solution is treated by ultrasonic treatment for 20 min to be completely dissolved. Blow-drying with nitrogen, and switching to an equivalent amount of chromatographic pure methanol solution.
(2) DBDPE photodegradation: 400. Mu.L of DBDPE standard solution was taken and irradiated with 150W high pressure mercury lamp ultraviolet light for 3 min in a 1.5 mL quartz glass bottle, which was placed at a horizontal distance of 10 cm and a vertical distance of 15 cm from the high pressure mercury lamp. The irradiated solution is filtered by an organic filter membrane with the thickness of 0.45 mu m to obtain degradation solution, and the degradation solution is transferred into a brown sample bottle to be detected.
(3) Qualitative detection of debromination products: detecting the DBDPE photodegradation product by HPLC-APPI-TOF/MS, adopting Agilent Eclipse XDB-C18 chromatographic column with specification of 150-mm long, diameter of 2.1-mm and filler particle of 3.5 μm; an Agilent XDB-C18 guard column (diameter 2.1 mm X column length 12.5 mm, packing particle size 5 μm) was provided; methanol is a mobile phase, and the flow rate is 0.3 mL/min; the column temperature of the chromatographic column is kept at 23+/-2 ℃; the sample injection volume is 2 mu L; in APPI - Based on [ M-Br+O ] in mode]And carrying out full scanning (scan) analysis on the characteristic ion peaks, wherein the scanning range m/z is 100-1000.
(4) And (3) separating and preparing a debrominated product: concentrating 25 ppm of DBDPE methanol standard solution to 40 ppm, separating and collecting DBDPE photodegradation sample by SP-HPLC, and adopting Agilent 5 TC-C18 (2) chromatographic column with specification of 150 mm length, diameter of 4.6 mm and filler particle of 5 μm; methanol is used as a mobile phase, and the flow rate is 0.8 mL/min; column temperature of the chromatographic column is 30 ℃; ultraviolet detection wavelength 230 nm.
Results: when the light is irradiated for 3 min, DBDPE can not be completely degraded, only nine-bromine and eight-bromine conversion products are detected, and the peak-to-peak type is poor; and the Agilent 5 TC-C18 (2) (4.6X106 mm,5 μm) chromatographic column is adopted, so that the retention time of the compound is shorter, the peak of the compound is not completely separated, and the effect is poor.
Example 4: the preparation, separation and purification method of decabromodiphenyl ethane debromination product comprises the following steps: (1) preparing DBDPE standard solution: the DBDPE standard with the mass fraction of 96% is dissolved in chromatographic pure toluene to prepare 25 ppm standard solution, and the standard solution is treated by ultrasonic treatment for 20 min to be completely dissolved. Blow-drying with nitrogen, and switching to an equivalent amount of chromatographic pure methanol solution.
(2) DBDPE photodegradation: 400. Mu.L of DBDPE standard solution was taken and irradiated with 150W high pressure mercury lamp ultraviolet light in a 1.5 mL quartz glass bottle for 5 min, the horizontal distance of the quartz glass bottle containing the standard solution and the high pressure mercury lamp was 10 cm, and the vertical distance was 15 cm. The irradiated solution is filtered by an organic filter membrane with the thickness of 0.45 mu m to obtain degradation solution, and the degradation solution is transferred into a brown sample bottle to be detected.
(3) Qualitative detection of debromination products: detecting the DBDPE photodegradation product by HPLC-APPI-TOF/MS, adopting Agilent Eclipse XDB-C18 chromatographic column with specification of 150-mm long, diameter of 2.1-mm and filler particle of 3.5 μm; an Agilent XDB-C18 guard column (diameter 2.1 mm X column length 12.5 mm, packing particle size 5 μm) was provided; methanol is a mobile phase, and the flow rate is 0.3 mL/min; the column temperature of the chromatographic column is kept at 23+/-2 ℃; the sample injection volume is 2 mu L; in APPI - Based on [ M-Br+O ] in mode]And carrying out full scanning (scan) analysis on the characteristic ion peaks, wherein the scanning range m/z is 100-1000.
(4) And (3) separating and preparing a debrominated product: concentrating 25 ppm of DBDPE methanol standard solution to 40 ppm, separating and collecting DBDPE photodegradation sample by SP-HPLC, and adopting Kromasil 100-5C18 chromatographic column with specification of length 250 mm, diameter 4.6 mm and filler particle of 5 μm; methanol is used as a mobile phase, and the flow rate is 0.8 mL/min; column temperature of the chromatographic column is 30 ℃; ultraviolet detection wavelength 230 nm.
Results: the compound can be separated from the peak by using a Kromasil 100-5C18 (4.6X1250 mm,5 μm) chromatographic column, but the peak type is poor, the overall peak appearance baseline is unstable, and the peak appearance time is late. FIG. 3 is a separation chromatogram of the DBDPE debrominated conversion products by SP-HPLC different columns.
The parts not described in the invention can be realized by referring to the prior art.
It will be appreciated by persons skilled in the art that the above embodiments have been provided for the purpose of illustration only and not as a definition of the limits of the present application, and that appropriate modifications and variations of the above embodiments are within the scope of the invention as claimed.
Claims (7)
1. The preparation, separation and purification method of decabromodiphenyl ethane debromination product is characterized by comprising the following steps in sequence:
step one, preparing a standard solution of decabromodiphenyl ethane;
step two, photodegradation of decabromodiphenyl ethane: taking 400 mu L of standard solution of decabromodiphenyl ethane in a quartz glass bottle, using high-pressure mercury lamp ultraviolet light to irradiate and degrade the standard solution, passing through a 0.45 mu m organic filter membrane to obtain degraded solution, and transferring the degraded solution into a brown sample bottle to be detected;
step three, detecting a debromination product: detecting a decabromodiphenylethane photodegradation product by adopting a high performance liquid chromatography mass spectrometer, and identifying a decabromodiphenylethane debromination product based on [ M-Br+O ] characteristic ion peaks in a negative ion mode;
and step four, separating and preparing a debromination product: separating and collecting photodegradation samples containing decabromodiphenyl ethane debromination products by adopting semi-preparative liquid chromatography; the semi-preparative liquid chromatography adopts Agilent Zorbax Eclipse PAH chromatographic column with the specification of 250 mm length, 4.6 mm diameter and 5 μm filler particles; methanol is used as a mobile phase, and the flow rate is 0.8 mL/min; the temperature of the chromatographic column is 30 ℃, 200 mu L of sample is injected each time, and the ultraviolet detection wavelength is 230 nm;
step five, weighing: the solution separated and collected in the fourth step is subjected to rotary concentration, and is dried by nitrogen, and then is weighed to obtain four low-bromine diphenyl ethane;
step six, purity measurement of the separated product: and (3) respectively dissolving the four low-brominated diphenylethanes obtained in the step five into methanol, and detecting the purity of the four low-brominated diphenylethanes by using a high performance liquid chromatography mass spectrometer to obtain 2 octabromodiphenylethane isomers with the purities of 82.38% and 88.76%, the purity of heptabromodiphenylethane of 97.83% and the purity of hexabromodiphenylethane of 92.19%.
2. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 1, characterized in that: in the first step, a decabromodiphenylethane standard substance with the mass fraction of 96% is placed in toluene solution, and is subjected to ultrasonic treatment to be completely dissolved, and then is dried by nitrogen, and is switched into methanol solution with the same amount as the toluene solution.
3. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 1, characterized in that: in the second step, the high-pressure mercury lamp is 150W, the horizontal distance between the quartz glass bottle for holding the standard solution and the high-pressure mercury lamp is 10 cm, the vertical distance is 15 cm, and the illumination time of the high-pressure mercury lamp is 5 min.
4. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 1, characterized in that: in the third step, the high performance liquid chromatography-atmospheric pressure photoionization-flight time mass spectrum is adopted as a high performance liquid chromatography-atmospheric pressure photoionization-flight time mass spectrum, a Agilent Eclipse XDB-C18 chromatographic column is adopted, the specification of the chromatographic column is 150 mm long, the diameter is 2.1 mm, and the filler particles are 3.5 mu m; methanol is a mobile phase with a flow rate of 0.3 mL/min; the column temperature of the chromatographic column is kept at 23+/-2 ℃ and 2 mu L of the chromatographic column is injected each time.
5. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 2, characterized in that: the concentration of the decabromodiphenylethane standard solution is 25 ppm, the ultrasonic power is 500 and W, and the treatment time is 20 min.
6. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 2, characterized in that: the toluene and the methanol are of chromatographic grade.
7. The method for preparing, separating and purifying decabromodiphenyl ethane debromination product according to claim 1, characterized in that: the purity of the four low-brominated diphenylethanes was quantitatively calculated by peak area.
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| CN101747910A (en) * | 2008-12-17 | 2010-06-23 | 第一毛织株式会社 | Mixtures of brominated diphenylethanes, method of preparing the same and resin composition using the same |
| CN102153440A (en) * | 2011-03-03 | 2011-08-17 | 山东天一化学股份有限公司 | Method for preparing octabromodiphenylethane |
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| CN101747910A (en) * | 2008-12-17 | 2010-06-23 | 第一毛织株式会社 | Mixtures of brominated diphenylethanes, method of preparing the same and resin composition using the same |
| CN102153440A (en) * | 2011-03-03 | 2011-08-17 | 山东天一化学股份有限公司 | Method for preparing octabromodiphenylethane |
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