CN102759593A - Chromatograph detection method for inorganic anions and cations in DOPO - Google Patents
Chromatograph detection method for inorganic anions and cations in DOPO Download PDFInfo
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- CN102759593A CN102759593A CN2012102534146A CN201210253414A CN102759593A CN 102759593 A CN102759593 A CN 102759593A CN 2012102534146 A CN2012102534146 A CN 2012102534146A CN 201210253414 A CN201210253414 A CN 201210253414A CN 102759593 A CN102759593 A CN 102759593A
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Abstract
The invention provides a chromatograph detection method for inorganic anions and cations in DOPO. The method provided by the invention includes the steps as follows: taking chloroform as an extracting agent; performing centrifugation for dissolved DOPO to obtain clear liquid; and adopting an automatic sampler-double-channel ion chromatography to synchronously detect inorganic anions and cations in DOPO, thereby greatly shortening the analysis time. According to the invention, the retention time RSD (n=6) of the inorganic anions and cations is 0.07% to 0.18%, the RSD (n=6) at the peak area is 0.43% to 0.88%, the repeatability is high, inorganic anions and cations in DOPO can be detected quickly, the purity of DOPO is controlled at an early stage, and the potential safety hazard of terminal products is reduced.
Description
Technical field
The invention belongs to and detect and analysis field, relate to the chromatographic detection method of inorganic zwitterion among the DOPO.
Background technology
DOPO (chemical name: 9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide) and be the BACN intermedium, have than general organophosphate thermal stability is high, chemical stability is high and the better advantage of fire resistance.DOPO and derivant thereof can be used as response type and additive flame retardant, synthetic fire retardant Halogen, smokeless, nontoxic, do not move, fire resistance is lasting.Can be used for multiple macromolecular material flame treatment such as linear polyester, polyamide, epoxy resin, polyurethane.The external electronic equipment that has been widely used in is with pressing the fire-retardant of materials such as layer, circuit board in plastics, the brass.
But DOPO can introduce a small amount of halogen or inorganic cation in synthetic process, the existence of these ions will certainly influence the purity of DOPO, increases the potential safety hazard of end product.
Summary of the invention
The invention provides the chromatographic detection method of inorganic zwitterion among the DOPO; Utilize detection method according to the invention can accomplish the detection of inorganic zwitterion among the DOPO in the short period; At the content that in earlier stage can monitor out inorganic zwitterion among the DOPO; Reduce user's loss, the maximization of guaranteeing the profit.
For realizing the foregoing invention purpose, the present invention adopts following technical proposals to be achieved:
The chromatographic detection method of inorganic zwitterion among the DOPO may further comprise the steps:
(1) pre-service
Take by weighing DOPO 1-2g, add chloroform 1～80mL, with ultrasound wave DOPO is dissolved, add deionized water 1～100mL then, sealing is acutely rocked, and the centrifuging and taking water layer is through solid-phase extraction column absorption and 0.22 μ m membrane filtration;
(2) chromatogram detects
Use the dual system ion chromatograph, will pass through the testing sample while sample detection zwitterion content that pre-service obtains, sample size 200 μ l;
The leacheate of anion chromatographic column: 0.5～5.0mM Na
2CO
3+ 0.5～5.0mM NaHCO
3, flow velocity: 1.0～1.5mL/min; Detecting device is led detection for suppressing electricity, suppresses electric current: 10～100mA;
The leacheate of cation chromatographic column: 1～48mM CH
3SO
3H, flow velocity: 0.6～1.0mL/min; Detecting device is led detection for suppressing electricity, suppresses electric current: 0～60mA;
(3) use calibration curve method, according to calculated by peak area zwitterion content.
Further improvement to technique scheme: said negative ion is Cl
-And SO
4 2-, said kation is Na
+
Further improvement to technique scheme: the filling material of anion chromatographic column is styrene and divinyl benzene copolymer, and ion exchange functional groups is a quaternary amine.
Further improvement to technique scheme: the filling material of cation chromatographic column is styrene and divinyl benzene copolymer, and ion exchange functional groups is a sulfonic group.
Further improvement to technique scheme: solid-phase extraction column is the octadecyl silane filler.
Further improvement to technique scheme: centrifugal condition is the centrifugal 1-30min of 4000r/min.
Further improvement to technique scheme: 5-10min is acutely rocked in sealing.
Further improvement to technique scheme: the anion chromatographic column length is 250mm, and internal diameter is 4.6mm, and the filling material particle diameter is 5-25 μ m.
Further improvement to technique scheme: the cation chromatography column length is 100mm, and internal diameter is 4.6mm, and the filling material particle diameter is 5-25 μ m.
Compared with prior art, advantage of the present invention and good effect are:
The present invention is extractant with the chloroform, and after the DOPO dissolving, centrifugal filtering liquid uses the inorganic zwitterion among automatic sampler-binary channels chromatography of ions synchronous detection DOPO, has shortened analysis time greatly.The retention time RSD of inorganic zwitterion (n=6) is 0.07%～0.18% among the present invention; The RSD of peak area (n=6) is 0.43%～0.88%, and reappearance is high, can fast detecting go out the inorganic zwitterion among the DOPO; In the purity of in earlier stage controlling DOPO, reduced the potential safety hazard of end product.
After advantages embodiment of the present invention, other characteristics of the present invention and advantage will become clearer.
Description of drawings
Fig. 1 is the process flow diagram of chromatographic detection method according to the invention.
Fig. 2 detects among the DOPO chlorion with the chromatogram of sulfate ion, wherein Cl among the present invention
-Concentration 6.927mg/L, SO
4 2-Concentration 0.539mg/L.
Fig. 3 is the chromatogram that detects sodion among the DOPO among the present invention, wherein Na
+Concentration 4.826mg/L.
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is done further detailed explanation.
Embodiment 1
The used instrument of the present invention is: PIC-10A binary channels ion chromatograph; PIC-JY automatic sampler (Qingdao Puren Instrument Co., Ltd.); Hydro-extractor (Shanghai hydro-extractor factory); PG-2010 countercharge workstation, supersonic wave cleaning machine (Kunshan Ultrasonic Instruments Co., Ltd.), pretreatment column and 0.22 μ m syringe needle filter membrane (Qingdao Puren Instrument Co., Ltd.).
The used reagent of the present invention is: Na
2CO
3, NaHCO
3, CH
3SO
3H, NaCl, Na
2SO
4(analyzing pure), above medicine are all available from those chemical reagent company limiteds of Shanghai dust, and all solution all adopt the ultrapure water preparation of 18.2M Ω .cm.
The chromatographic detection method of inorganic zwitterion specifically may further comprise the steps among the DOPO according to the invention:
1. preprocess method
(1) add about DOPO 1g (being accurate to 0.1mg) in pipe (the FEP system has lid 50mL) lining, Shen far away, chloroform 1.5mL dissolves DOPO with supersonic wave cleaning machine.
(2) with after the DOPO dissolving, add deionized water 8.5mL, the lid lid is tight, prevent seepage.
(3) Shen far away pipe is carried out acutely rocking of 5-10min, separates with hydro-extractor again, 4000r/min10min, centrifugal after, chloroform separates with water layer.
(4) water intaking layer after organic substance is removed in solid-phase extraction column (octadecyl silane) absorption, is removed impurity, the zwitterion concentration that sample detection contains through 0.22 μ m membrane filtration.
2. chromatogram detects
The chromatogram testing process is as shown in Figure 1, may further comprise the steps:
(1) prepares leacheate, open high pressure constant-flux pump and ion chromatograph power supply;
Anion chromatographic column (250mm * 4.6mm): filling material is styrene and divinyl benzene copolymer, and ion exchange functional groups is a quaternary amine, and leacheate is: 0.5mM Na
2CO
3+ 0.5mM NaHCO
3, flow velocity: 1.0mL/min.Detecting device: electric conductivity detector, suppress electric current: 10mA.Sample detection.
Cation chromatographic column (100mm * 4.6mm): filling material is styrene and divinyl benzene copolymer, and ion exchange functional groups is a sulfonic group, leacheate: 40mM CH
3SO
3H, flow velocity: 0.6mL/min.Detecting device: electric conductivity detector, suppress electric current: 10mA.Sample detection.
(2) leacheate washes chromatographic column, rejector and electric conductivity detector under 0.8-1.5mL/min, washes after 0.5～2 hour the direct current that applies 10mA to rejector;
(3) when showing that the gear voltage value does not have significant change in the chromatographic work station, pretreated sample input ion chromatograph to be analyzed, sample size is 200 μ l.
Through comparing, according to the concentration of calculated by peak area zwitterion with typical curve.
3. experimental result
3.1 drawing standard curve
Preparation 1000mg/L chlorion standard reserving solution: accurately take by weighing the dry NaCl solid of 0.8245g in the 50ml glass beaker; Be transferred in the 500ml volumetric flask after the ultrapure water dissolving; Repeatedly clean the beaker inwall with ultrapure water, cleaning fluid is transferred to volumetric flask equally, is settled to 500ml at last.
Preparation 1000mg/L sulfate radical standard reserving solution: accurately take by weighing the dry Na of 0.7395g
2SO
4Solid is transferred in the 500ml volumetric flask after the ultrapure water dissolving in the 50ml glass beaker, repeatedly cleans the beaker inwall with ultrapure water, and cleaning fluid is transferred to volumetric flask equally, is settled to 500ml at last.
Preparation 1000mg/L sodion standard reserving solution: accurately take by weighing the dry NaCl solid of 1.2740g in the 50ml glass beaker; Be transferred in the 500ml volumetric flask after the ultrapure water dissolving; Repeatedly clean the beaker inwall with ultrapure water, cleaning fluid is transferred to volumetric flask equally, is settled to 500ml at last.
Pipette chlorion standard reserving solution and each 1.0ml of sulfate radical standard reserving solution, place the 100ml volumetric flask and use the ultrapure water constant volume.The concentration of chlorion and sulfate radical is 10mg/L in this solution.Pipette this solution 0.5,2.0,5.0,10.0,25.0ml respectively and in 5 100ml volumetric flasks, also use the ultrapure water constant volume.Obtained the mixed standard solution series of chlorion and sulfate radical.
Pipette sodion standard reserving solution 1.0ml, place the 100ml volumetric flask and use the ultrapure water constant volume.The concentration of sodion is 10mg/L in this solution.Pipette this solution 0.5,2.0,5.0,10.0,25.0ml respectively and in 5 100ml volumetric flasks, also use the ultrapure water constant volume.Obtained the standard solution series of sodion.
Under the described chromatogram testing conditions of step 2, the standard solution series of above-mentioned chlorion, sulfate radical and sodion is imported ion chromatograph analysis successively.Calculate minimum detectability with 3 times signal to noise ratio (S/N ratio)s (S/N=3).The linear equation of three kinds of ions, related coefficient and minimum detectability (n=3), the result sees table 1.
Table 1Cl
-, SO
4 2-And Na
+Linear equation, related coefficient and minimum detectability
3.2 zwitterion concentration in the calculating sample
Under the described chromatogram testing conditions of step 2, said negative ion and cation chromatography detect collection of illustrative plates shown in Fig. 2 and 3, and Fig. 2 and Fig. 3 show and mainly have Cl among the DOPO
-, SO
4 2-And Na
+Three kinds of ions, the content that calculates three kinds of ions with the external standard method typical curve is respectively 6.927mg/L, 0.539mg/L and 4.826mg/L.Kation (Na
+) electrically charged quantity is negative ion (Cl
-, SO
4 2-) electrically charged number 101.7%, this method extraction gained ionic substance charge conservation is described.
3.3 recovery of standard addition
In pretreated gained sample, add 5.0mg/LCl
-, 0.5mg/LSO
4 2-, 5.0mg/LNa
+, under the chromatography of ions condition of confirming, carry out the mark-on recovery test, sample replicate determination 3 times.Experimental result is as shown in table 2.
Table 2 sample recovery of standard addition
3.4 reappearance test
According to 6 parts in preprocess method parallel processing DOPO sample, the retention time of three kinds of ions and peak area reappearance result are as shown in table 3.Can find out that from table 3 this method is reliable and stable, favorable reproducibility.
Table 3 retention time and peak area reappearance result
Detection method according to the invention with water extraction inorganic zwitterion wherein, is used automatic sampler-binary channels ion chromatography inorganic zwitterion wherein with dissolved in chloroform DOPO.Experimental result shows, mainly has Cl among the DOPO
-(6.927mg/L), SO
4 2-(0.539mg/L) and Na
+(4.826mg/L) three kinds of ions.Said method extraction gained ionic charge conservation, recovery of standard addition is high, and three kinds of ions are that retention time or peak area all have higher reappearance, for the analysis of inorganic zwitterion among the DOPO provides reliable method.
Above embodiment is only in order to explaining technical scheme of the present invention, but not limits it; Although the present invention has been carried out detailed explanation with reference to previous embodiment, for the person of ordinary skill of the art, still can make amendment to the technical scheme that previous embodiment is put down in writing, perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of relevant art scheme break away from the spirit and the scope of the present invention's technical scheme required for protection.
Claims (9)
1.DOPO the chromatographic detection method of middle inorganic zwitterion is characterized in that it may further comprise the steps:
(1) pre-service
Take by weighing DOPO1-2g, add chloroform 1～80mL, with ultrasound wave DOPO is dissolved, add deionized water 1～100mL then, sealing is acutely rocked, and the centrifuging and taking water layer is through solid-phase extraction column absorption and 0.22 μ m membrane filtration;
(2) chromatogram detects
Use the dual system ion chromatograph, will pass through the testing sample while sample detection zwitterion content that pre-service obtains, sample size 200 μ l;
The leacheate of anion chromatographic column: 0.5～5.0mM Na
2CO
3+ 0.5～5.0mM NaHCO
3, flow velocity: 1.0～1.5mL/min; Detecting device is led detection for suppressing electricity, suppresses electric current: 10～100mA;
The leacheate of cation chromatographic column: 1～48mM CH
3SO
3H, flow velocity: 0.6～1.0mL/min; Detecting device is led detection for suppressing electricity, suppresses electric current: 0～60mA;
(3) use calibration curve method, according to calculated by peak area zwitterion content.
2. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 1 is characterized in that said negative ion is Cl
-And SO
4 2-, said kation is Na
+
3. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 1 and 2, the filling material that it is characterized in that anion chromatographic column is styrene and divinyl benzene copolymer, ion exchange functional groups is a quaternary amine.
4. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 1 and 2, the filling material that it is characterized in that cation chromatographic column is styrene and divinyl benzene copolymer, ion exchange functional groups is a sulfonic group.
5. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 2 is characterized in that said solid-phase extraction column is the octadecyl silane filler.
6. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 2 is characterized in that said centrifugal condition is the centrifugal 1-30min of 4000r/min.
7. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 2 is characterized in that sealing and acutely rocks 5-10min.
8. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 3 is characterized in that the anion chromatographic column length is 250mm, and internal diameter is 4.6mm, and the filling material particle diameter is 5-25 μ m.
9. the chromatographic detection method of inorganic zwitterion among the DOPO according to claim 4 is characterized in that the cation chromatography column length is 100mm, and internal diameter is 4.6mm, and the filling material particle diameter is 5-25 μ m.
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| CN105203691A (en) * | 2015-10-15 | 2015-12-30 | 上海天洋热熔粘接材料股份有限公司 | Analysis determination method for special phosphate-containing fire retardant in copolyester hot-melt adhesive netted film |
| CN106596770A (en) * | 2016-12-13 | 2017-04-26 | 四川大学 | Low-pressure anion-cation chromatographic-spectrophotometric method for simultaneous online automatic analysis of trace ammonium ions and nitrite ions in water sample |
| CN109342638A (en) * | 2018-11-29 | 2019-02-15 | 浙江树人学院 | A method of detecting nitrile, quaternary ammonium salt and its impurity ammonium, potassium, calcium ion content in blocking using cation exchange inhibition conductance method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105158123A (en) * | 2015-08-31 | 2015-12-16 | 武汉宇虹环保产业发展有限公司 | Online environmental air fine particle water-soluble ion chromatograph |
| CN105203691A (en) * | 2015-10-15 | 2015-12-30 | 上海天洋热熔粘接材料股份有限公司 | Analysis determination method for special phosphate-containing fire retardant in copolyester hot-melt adhesive netted film |
| CN106596770A (en) * | 2016-12-13 | 2017-04-26 | 四川大学 | Low-pressure anion-cation chromatographic-spectrophotometric method for simultaneous online automatic analysis of trace ammonium ions and nitrite ions in water sample |
| CN106596770B (en) * | 2016-12-13 | 2019-03-29 | 四川大学 | Simultaneously in on-line automatic analysis water-like micro ammonium ion and nitrite ion low pressure anions and canons chromatography-photometry |
| CN109342638A (en) * | 2018-11-29 | 2019-02-15 | 浙江树人学院 | A method of detecting nitrile, quaternary ammonium salt and its impurity ammonium, potassium, calcium ion content in blocking using cation exchange inhibition conductance method |
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