CN102759593B - Chromatograph detection method for inorganic anions and cations in DOPO - Google Patents

Chromatograph detection method for inorganic anions and cations in DOPO Download PDF

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CN102759593B
CN102759593B CN201210253414.6A CN201210253414A CN102759593B CN 102759593 B CN102759593 B CN 102759593B CN 201210253414 A CN201210253414 A CN 201210253414A CN 102759593 B CN102759593 B CN 102759593B
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dopo
detection method
zwitterion
chromatographic
inorganic
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CN102759593A (en
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杜晓磊
王存进
张世忠
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QINGDAO PUREN INSTRUMENT CO Ltd
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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

The chromatographic detection method of inorganic zwitterion in DOPO
Technical field
The invention belongs to examination and analysb field, relate to the chromatographic detection method of inorganic zwitterion in DOPO.
Background technology
DOPO(chemical name: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) be BACN intermediate, have higher than general organophosphate thermal stability, 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, the fire retardant Halogen of synthesis, smokeless, nontoxic, do not move, fire resistance is lasting.Can be used for the multiple macromolecular material flame treatment such as linear polyester, polyamide, epoxy resin, polyurethane.External being widely used in plastics for electronics, brass presses the fire-retardant of the material such as layer, circuit board.
But DOPO can introduce a small amount of halogen or inorganic cation in the process of synthesis, and the existence of these ions will certainly affect the purity of DOPO, increase the potential safety hazard of end product.
Summary of the invention
The invention provides the chromatographic detection method of inorganic zwitterion in DOPO, utilize detection method of the present invention can complete the detection of inorganic zwitterion in DOPO in the short period, the content of inorganic zwitterion in DOPO can be monitored out in early stage, reduce the loss of user, the maximization of guaranteeing the profit.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The chromatographic detection method of inorganic zwitterion in DOPO, comprises the following steps:
(1) pre-service
Take DOPO 1-2g, add chloroform 1 ~ 80mL, dissolved by DOPO with ultrasound wave, then add deionized water 1 ~ 100mL, sealing is acutely rocked, centrifuging and taking water layer, through solid-phase extraction column absorption and 0.22 μm of membrane filtration;
(2) chromatogram detects
Use dual system ion chromatograph, by the testing sample sample detection zwitterion content simultaneously obtained through pre-service, 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 Suppressor conductivity detection, 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 Suppressor conductivity detection, suppresses electric current: 0 ~ 60mA;
(3) calibration curve method is used, according to calculated by peak area zwitterion content.
Further improvement to technique scheme: described negative ion is Cl -and SO 4 2-, described 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 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 sulfonic group.
Further improvement to technique scheme: solid-phase extraction column is octadecyl silane filler.
Further improvement to technique scheme: centrifugal condition is the centrifugal 1-30min of 4000r/min.
Further improvement to technique scheme: sealing acutely rocks 5-10min.
Further improvement to technique scheme: anion chromatographic column length is 250mm, internal diameter is 4.6mm, and filling material particle diameter is 5-25 μm.
Further improvement to technique scheme: cation chromatography column length is 100mm, internal diameter is 4.6mm, and filling material particle diameter is 5-25 μm.
Compared with prior art, advantage of the present invention and good effect are:
The present invention take chloroform as extractant, and after being dissolved by DOPO, centrifugal filtering liquid, use automatic sampler-binary channels chromatography of ions synchronously detects the inorganic zwitterion in DOPO, substantially reduces analysis time.In the present invention, the retention time RSD (n=6) of inorganic zwitterion is 0.07% ~ 0.18%, the RSD (n=6) of peak area is 0.43% ~ 0.88%, reappearance is high, the inorganic zwitterion in DOPO can be detected fast, in the purity of beforehand control DOPO, reduce the potential safety hazard of end product.
After reading the specific embodiment of the present invention by reference to the accompanying drawings, the other features and advantages of the invention will become clearly.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of chromatographic detection method of the present invention.
Fig. 2 detects chlorion in DOPO to follow the chromatogram of sulfate ion, wherein Cl in the present invention -concentration 6.927mg/L, SO 4 2-concentration 0.539mg/L.
Fig. 3 is the chromatogram detecting sodion in DOPO in the present invention, wherein Na +concentration 4.826mg/L.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
Embodiment 1
The present invention's instrument used is: PIC-10A binary channels ion chromatograph, PIC-JY automatic sampler (Qingdao Puren Instrument Co., Ltd.), hydro-extractor (Shanghai hydro-extractor factory), PG-2010 countercharges workstation, supersonic wave cleaning machine (Kunshan Ultrasonic Instruments Co., Ltd.), pretreatment column and 0.22 μm of syringe needle filter membrane (Qingdao Puren Instrument Co., Ltd.).
The present invention's reagent used is: Na 2cO 3, NaHCO 3, CH 3sO 3h, NaCl, Na 2sO 4(analyzing pure), above medicine is all purchased from Shanghai Ai Bi chemical reagent company limited, and all solution all adopts the ultrapure water of 18.2M Ω .cm to prepare.
In DOPO of the present invention, the chromatographic detection method of inorganic zwitterion specifically comprises the following steps:
1. preprocess method
(1) Shen far away pipe (FEP system has lid 50mL) the inner DOPO of adding about 1g (being accurate to 0.1mg), chloroform 1.5mL, dissolves DOPO with supersonic wave cleaning machine.
(2), after DOPO being dissolved, add deionized water 8.5mL, lid is covered tightly, prevent seepage.
(3) Shen far away pipe is carried out acutely rocking of 5-10min, then be separated with hydro-extractor, 4000r/min10min, after centrifugal, chloroform is separated with water layer.
(4) water intaking layer, after solid-phase extraction column (octadecyl silane) absorption removing organic substance, through 0.22 μm of membrane filtration removing impurity, the zwitterion concentration that sample detection contains.
2. chromatogram detects
Chromatogram testing process as shown in Figure 1, comprises the following steps:
(1) prepare 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, ion exchange functional groups is quaternary amine, and leacheate is: 0.5mM Na 2cO 3+ 0.5mM NaHCO 3, flow velocity: 1.0mL/min.Detecting device: electric conductivity detector, suppresses electric current: 10mA.Sample detection.
Cation chromatographic column (100mm × 4.6mm): filling material is styrene and divinyl benzene copolymer, ion exchange functional groups is sulfonic group, leacheate: 40mM CH 3sO 3h, flow velocity: 0.6mL/min.Detecting device: electric conductivity detector, suppresses electric current: 10mA.Sample detection.
(2) leacheate rinses chromatographic column, rejector and electric conductivity detector under 0.8-1.5mL/min, rinses the direct current applying 10mA after 0.5 ~ 2 hour to rejector;
(3) when showing gear voltage value in chromatographic work station and not having significant change, analyzed by pretreated sample input ion chromatograph, sample size is 200 μ l.
By comparing with typical curve, according to the concentration of calculated by peak area zwitterion.
3. experimental result
3.1 drawing standard curves
Preparation 1000mg/L chlorion standard reserving solution: accurately take the NaCl solid of 0.8245g drying in 50ml glass beaker, ultrapure water is transferred in 500ml volumetric flask after dissolving, repeatedly clean beaker inwall with ultrapure water, cleaning fluid is transferred to volumetric flask equally, is finally settled to 500ml.
Preparation 1000mg/L sulfate radical standard reserving solution: the Na accurately taking 0.7395g drying 2sO 4solid is in 50ml glass beaker, and ultrapure water is transferred in 500ml volumetric flask after dissolving, and repeatedly clean beaker inwall with ultrapure water, cleaning fluid is transferred to volumetric flask equally, is finally settled to 500ml.
Preparation 1000mg/L sodion standard reserving solution: accurately take the dry NaCl solid of 1.2740g in 50ml glass beaker, ultrapure water is transferred in 500ml volumetric flask after dissolving, repeatedly clean beaker inwall with ultrapure water, cleaning fluid is transferred to volumetric flask equally, is finally settled to 500ml.
Pipette chlorion standard reserving solution and each 1.0ml of sulfate radical standard reserving solution, be placed in 100ml volumetric flask and use ultrapure water constant volume.The concentration of this Chlorine in Solution ion and sulfate radical is 10mg/L.Pipette respectively this solution 0.5,2.0,5.0,10.0,25.0ml is in 5 100ml volumetric flasks and use ultrapure water constant volume.Obtain the mixed standard solution series of chlorion and sulfate radical.
Pipette sodion standard reserving solution 1.0ml, be placed in 100ml volumetric flask and use ultrapure water constant volume.The concentration of this sodium ion in liquor is 10mg/L.Pipette respectively this solution 0.5,2.0,5.0,10.0,25.0ml is in 5 100ml volumetric flasks and use ultrapure water constant volume.Obtain the standard solution series of sodion.
Under chromatographic test strip part described in step 2, the standard solution series of above-mentioned chlorion, sulfate radical and sodion is inputted ion chromatograph analysis successively.Minimum detectability is calculated with the signal to noise ratio (S/N ratio) of 3 times (S/N=3).The linear equation of three kinds of ions, related coefficient and minimum detectability (n=3), the results are shown in Table 1.
Table 1Cl -, SO 4 2-and Na +linear equation, related coefficient and minimum detectability
3.2 calculate zwitterion concentration in sample
Under chromatographic test strip part described in step 2, described negative ion and cation chromatography detect collection of illustrative plates as shown in Figures 2 and 3, Fig. 2 and Fig. 3 shows mainly there is Cl in DOPO -, SO 4 2-and Na +three kinds of ions, the content calculating three kinds of ions with 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%, the method extraction gained ionic substance charge conservation is described.
3.3 recovery of standard addition
5.0mg/LCl is added in pretreated gained sample -, 0.5mg/LSO 4 2-, 5.0mg/LNa +, under the chromatography of ions condition determined, carry out mark-on recovery test, sample parallel measures 3 times.Experimental result is as shown in table 2.
Table 2 sample recovery of standard addition
3.4 reappearance tests
According to 6 parts, preprocess method parallel processing DOPO sample, retention time and the peak area reappearance result of three kinds of ions are as shown in table 3.This method is reliable and stable as can be seen from Table 3, favorable reproducibility.
Table 3 retention time and peak area reappearance result
Detection method of the present invention dissolves DOPO with chloroform, with water extraction inorganic zwitterion wherein, uses automatic sampler-binary channels ion chromatography inorganic zwitterion wherein.Experimental result shows, mainly there is Cl in DOPO -(6.927mg/L), SO 4 2-(0.539mg/L) and Na +(4.826mg/L) three kinds of ions.Described 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, in DOPO, the analysis of inorganic zwitterion provides reliable method.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.

Claims (6)

  1. The chromatographic detection method of inorganic zwitterion in 1.DOPO, is characterized in that it comprises the following steps:
    (1) pre-service
    Take DOPO1g, add chloroform 1.5mL, dissolved by DOPO with ultrasound wave, then add deionized water 8.5mL, sealing is acutely rocked, centrifuging and taking water layer, through solid-phase extraction column absorption and 0.22 μm of membrane filtration;
    (2) chromatogram detects
    Use dual system ion chromatograph, by the testing sample sample detection zwitterion content simultaneously obtained through pre-service, sample size 200 μ l;
    The leacheate of anion chromatographic column: 0.5mM Na 2cO 3+ 0.5mM NaHCO 3, flow velocity: 1.0mL/min; Detecting device is Suppressor conductivity detection, suppresses electric current: 10mA;
    The leacheate of cation chromatographic column: 40mM CH 3sO 3h, flow velocity: 0.6mL/min; Detecting device is Suppressor conductivity detection, suppresses electric current: 10mA;
    (3) calibration curve method is used, according to calculated by peak area zwitterion content;
    Described negative ion is Cl -and SO 4 2-, described kation is Na +;
    The filling material of anion chromatographic column is styrene and divinyl benzene copolymer, and ion exchange functional groups is quaternary amine;
    The filling material of cation chromatographic column is styrene and divinyl benzene copolymer, and ion exchange functional groups is sulfonic group.
  2. 2. the chromatographic detection method of inorganic zwitterion in DOPO according to claim 1, is characterized in that described solid-phase extraction column is octadecyl silane filler.
  3. 3. the chromatographic detection method of inorganic zwitterion in DOPO according to claim 1, is characterized in that described centrifugal condition is the centrifugal 1-30min of 4000r/min.
  4. 4. the chromatographic detection method of inorganic zwitterion in DOPO according to claim 1, is characterized in that sealing acutely rocks 5-10min.
  5. 5. the chromatographic detection method of inorganic zwitterion in DOPO according to claim 1, it is characterized in that anion chromatographic column length is 250mm, internal diameter is 4.6mm, and filling material particle diameter is 5-25 μm.
  6. 6. the chromatographic detection method of inorganic zwitterion in DOPO according to claim 1, it is characterized in that cation chromatography column length is 100mm, internal diameter is 4.6mm, and filling material particle diameter is 5-25 μm.
CN201210253414.6A 2012-07-20 2012-07-20 Chromatograph detection method for inorganic anions and cations in DOPO Active CN102759593B (en)

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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
CN105203691B (en) * 2015-10-15 2017-06-13 上海天洋热熔粘接材料股份有限公司 The analysis determining method of extraordinary phosphonium flame retardant in copolyester hot melt adhesive nethike embrane
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
CN109342638B (en) * 2018-11-29 2020-08-18 浙江树人学院 Method for detecting content of nitrile, quaternary ammonium salt and impurities ammonium, potassium and sodium ions in nitrile and quaternary ammonium salt by using cation exchange inhibition conductivity method

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