CN110806474A - Qualitative and quantitative detection method for red phosphorus in plastic product - Google Patents
Qualitative and quantitative detection method for red phosphorus in plastic product Download PDFInfo
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- G01N33/44—Resins; rubber; leather
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Abstract
The invention discloses a qualitative and quantitative detection method for red phosphorus in a plastic product. The invention adopts microscopic image analysis, a cracking gas chromatography-mass spectrometry combined method and XRF and ICP-OES combined method to determine the red phosphorus content in the plastic product. The detection method can be used for rapidly, accurately and visually observing the red phosphorus particles in the plastic product, is simple in pretreatment method, avoids introducing unnecessary interference, can be used for more accurately eliminating the interference of other phosphorus-containing substances in the sample by combining the quantitative analysis of the red phosphorus, and is high in detection efficiency and good in reproducibility.
Description
Technical Field
The invention relates to the field of red phosphorus detection, in particular to a qualitative and quantitative detection method for red phosphorus in a plastic product.
Background
Red phosphorus can enter human body through inhalation, ingestion and skin contact, and chronic phosphorus poisoning can be caused by frequent ingestion of red phosphorus dust; prolonged skin contact can cause dermatitis. The red phosphorus has certain toxicity to aquatic organisms and can cause problems of water eutrophication and the like. Many electronic and electrical enterprises in europe, america, japan, korea, etc. put red phosphorus into the environmental management standards of products, and some have set usage limits and some even have no use. In addition, many countries have also established regulatory standards for red phosphorus in workplace environments. Therefore, it is necessary to establish a suitable method for qualitative and quantitative analysis of red phosphorus in the product.
CN201610435434.3 discloses a method for testing the content of red phosphorus in a polymer, wherein a TG-FTIR-GC/MS triple combination is adopted for testing the content of red phosphorus in the polymer, cracked gas after cracking in TG continuously enters FT-IR and GC/MS for real-time testing, and absorption peaks of the cracked gas at different time points can be analyzed through a spectrogram continuously measured by the FT-IR, so that the interference of an organophosphorus flame retardant is effectively eliminated; the preliminary characterization of red phosphorus can be carried out through a GC/MS mass spectrogram and an ion spectrogram, and the cracking temperature point of red phosphorus can be found out; and (3) separating and measuring the sample cracked gas according to the temperature point calculated in the triple on-line mode, extracting the cracked gas at the temperature point section, entering the cracked gas into a chromatographic column, performing a temperature rise program, and quantitatively analyzing the sample according to the chromatographic peak height under the retention time of red phosphorus. The method has the advantages of direct sampling and testing, reduction of pretreatment process, and reduction of the risk of judging false positive.
CN201610069787.6 discloses a method for measuring red phosphorus content, which at least comprises the following steps: preparing the sample into powder; then soaking and ultrasonically treating the sample powder by using an organic reagent; soaking and ultrasonically treating the sample powder by using dilute acid; then washing with third-stage water and naturally drying; taking a trace amount of treated sample to perform a red phosphorus qualitative test in a cracking-gas chromatography/mass spectrometer; taking a proper amount of the treated sample to be digested into phosphate, and carrying out quantitative test on red phosphorus by using an inductively coupled plasma emission spectrometer. The method for determining the content of the red phosphorus in the plastic has the advantages that the method for removing the organic phosphorus and the inorganic phosphorus by pretreatment is adopted, the influence of the organic phosphorus and the inorganic phosphorus on the detection result can be greatly reduced, the detection limit of qualitative and quantitative test of the red phosphorus is reduced, and a feasible detection means is provided for determining whether the red phosphorus is contained in the production, molding and sale of the plastic.
CN200910078942.0 discloses a method for measuring the content of red phosphorus in an electronic material, wherein the red phosphorus in a sample to be measured reacts with a NaOH solution with the concentration of 10% in a headspace bottle to generate phosphine gas (PH)3) The red phosphorus was identified by measuring the Retention Time (RT) of the generated phosphine gas by a gas chromatograph-flame photometer, and then quantitatively analyzed by an external standard curve method. The method is used for detecting electricityThe content of red phosphorus in the sub-materials is quick and effective, and the relative standard deviation is not more than 10%.
However, the detection method cannot visually observe red phosphorus particles, unnecessary interference is easily introduced after the sample is treated by the pretreatment method, and when other organic phosphorus compounds are contained in the sample, the sample cannot be distinguished, so that the accuracy of the detection result is affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a qualitative and quantitative detection method for red phosphorus in a plastic product.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a qualitative and quantitative detection method for red phosphorus in a plastic product comprises the following steps:
(1) judging whether the sample contains phosphorus element by X fluorescence spectrum analysis (XRF);
(2) if the sample does not contain phosphorus, carrying out quantitative analysis on the phosphorus by inductively coupled plasma emission spectrometry (ICP-OES); if the sample contains phosphorus elements, whether the sample contains red phosphorus particles is judged through microscopic image analysis;
(3) if the sample does not contain red phosphorus particles, carrying out quantitative analysis on phosphorus by adopting ICP-OES; if the sample contains red phosphorus particles, the red phosphorus in the sample is qualitatively and quantitatively analyzed by adopting pyrolysis gas chromatography mass spectrometry, and then the phosphorus element is quantitatively analyzed by adopting ICP-OES.
The invention adopts microscopic image analysis, a cracking gas chromatography-mass spectrometry combined method and XRF and ICP-OES combined method to determine the red phosphorus content in the plastic product. The detection method can quickly, accurately and visually detect the red phosphorus content in the plastic product, and has high efficiency and good reproducibility.
Preferably, the test conditions of the X-fluorescence spectroscopy are: the collimator is 10 mm; analyzing the content of elements between Ti and U under the conditions of tube voltage of 50kV and tube current of 37 muA, and testing for 60 s; analyzing the content of elements between Al and Sc under the conditions of tube voltage of 50kV and tube current of 396 mu A, and testing for 60 s; analyzing the content of elements between S and Ca under the conditions of tube voltage of 50kV and tube current of 676 mu A, and testing for 60S; and a vacuum pumping mode is adopted.
When the XRF result shows that the sample contains phosphorus, the sample is proved to possibly contain red phosphorus or other organic phosphorus substances, whether the sample contains the red phosphorus or not needs to be verified by combining microscope image analysis, a pyrolysis gas chromatography-mass spectrometry combined method and ICP-OES, and the XRF can semi-quantitatively provide quantitative reference data for subsequent ICP-OES tests so as to avoid repeatedly diluting the sample.
When the XRF result shows that the sample does not contain phosphorus, the sample does not contain red phosphorus or other organic phosphorus, only the ICP detection limit is 10ppm, verification is carried out, subsequent analysis such as microscopic image analysis, cracking gas chromatography-mass spectrometry and the like is not needed, the red phosphorus sample can be rapidly screened, and time and efficiency are saved for testing.
Preferably, the magnification in the analysis of the microscope image is 800-1000 times.
Preferably, the inductively coupled plasma emission spectrometry comprises the following specific steps:
1) shearing a sample, adding a digestion reagent, and placing the sample in a microwave digestion instrument for digestion, wherein the digestion procedure is as follows: heating to 140 ℃ for 15min, keeping for 10min, heating to 180 ℃ for 10min, keeping for 10min, heating to 200 ℃ for 10min, keeping for 5min, and fixing the volume to obtain a sample solution to be measured;
2) measuring a phosphorus element working curve solution by using an inductively coupled plasma emission spectrometer, drawing a standard working curve, then measuring the concentration of phosphorus element in a sample solution to be measured, and when the concentration of the solution exceeds the highest point of the curve, diluting the sample solution to be measured and measuring again;
wherein the test conditions are as follows: the radio frequency power is 1300W, the observation direction is axial observation, the flow rate of the atomizer is 0.7L/min, the flow rate of the auxiliary gas is 0.2L/min, the flow rate of the plasma gas is 12L/min, the analysis pump speed is 1.0mL/min, and the analysis spectral line is 213.617 nm.
Under the test conditions, the standard solutions with different concentrations are analyzed, the detection limit (3 times of signal to noise ratio) of red phosphorus reaches 10ppm, the blank test result is less than the detection limit, and the test requirement of red phosphorus can be met.
Preferably, the test conditions of the pyrolysis gas chromatography mass spectrometry are as follows:
the gas phase conditions were: a chromatographic column: DB-5 MS; temperature rising procedure: maintaining at 50 deg.C for 2min, increasing to 80 deg.C at a rate of 10 deg.C/min, maintaining for 1min, increasing to 310 deg.C at a rate of 15 deg.C/min, and maintaining for 5 min; sample inlet temperature: 300 ℃; sample introduction mode: the split ratio is 1: 100; carrier gas: helium with purity more than or equal to 99.999%; flow rate: 3 mL/min;
the mass spectrum parameters are as follows: ion source temperature: 230 ℃; interface temperature of chromatography-mass spectrometry: 250 ℃; an ionization mode: electron bombardment ionization; ionization energy: 70 eV; solvent delay time: 0.5 min; an acquisition mode: SCAN; SCAN mass SCAN range: 29-600 m/z;
the temperature of the cracker is 550-650 ℃.
Under the optimized gas chromatography-mass spectrometry analysis conditions, red phosphorus can be well separated within 14min, the peak shape is symmetrical, and the matrix interference is small.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention establishes an analysis and test method for determining the content of red phosphorus in a plastic product by adopting a microscopic image, a pyrolysis gas chromatography-mass spectrometry combined method and XRF and ICP-OES.
(2) The invention can carry out element primary screening through XRF, can provide content range information for subsequent quantitative results, can directly carry out ICP analysis when carrying out qualitative test, if no phosphorus content exists, does not need to carry out subsequent analysis such as a microscope, cracking gas and the like, can quickly screen red phosphorus samples, and saves time and efficiency for testing.
(3) The detection method can simply, conveniently and intuitively observe the red phosphorus particles through an optical microscope or an electron microscope, more efficiently and intuitively detect whether the sample contains red phosphorus, and can more accurately eliminate the interference of other phosphorus-containing substances by combining the quantitative analysis of the content of the red phosphorus.
(4) The quantitative method of the invention has good reproducibility and can reach the detection limit of 10 ppm.
Drawings
FIG. 1 is a flow chart of the detection method of the present invention.
Fig. 2 shows the results of XRF elemental analysis of positive samples.
Fig. 3 is an electron microscope picture of a positive sample.
FIG. 4 is a chromatogram of the cracked gas of red phosphorus.
FIG. 5 is a mass spectrum of red phosphorus.
FIG. 6 is a cracked gas chromatogram of a positive sample.
FIG. 7 is a mass spectrum of a positive sample.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
A qualitative and quantitative detection method for red phosphorus in plastic products is shown in figure 1 and comprises the following steps:
(1) judging whether the sample contains phosphorus element or not through X fluorescence spectrum analysis;
(2) if the sample does not contain phosphorus, carrying out quantitative analysis on the phosphorus by using an inductively coupled plasma emission spectrometry; if the sample contains phosphorus elements, whether the sample contains red phosphorus particles is judged through microscopic image analysis;
(3) if the sample does not contain red phosphorus particles, carrying out quantitative analysis on phosphorus by adopting an inductively coupled plasma emission spectrometry; if the sample contains red phosphorus particles, the red phosphorus in the sample is qualitatively and quantitatively analyzed by adopting pyrolysis gas chromatography-mass spectrometry, and then the phosphorus element is quantitatively analyzed by adopting an over-inductive coupling plasma emission spectrometry.
In the present invention, the test conditions of the X fluorescence spectrum analysis are: the collimator is 10 mm; analyzing the element content between Al and Sc under the conditions that the tube voltage is 50kV and the tube current is 396 muA, and the testing time is 60 s; when the vacuum-pumping mode is adopted, leakage detection containing a small amount of phosphorus is easily caused when the vacuum-pumping-free mode is used for X fluorescence spectrum analysis.
In the invention, the amplification factor in the microscope image analysis is 500-1000 times, and the number of red phosphorus particles in the ocular lens is most obvious between 10 and 30. When the magnification is less than 500 times, the appearance of which substance is difficult to observe after the red phosphorus particles are coated. Above 1000 times, the distribution of red phosphorus particles in the ocular lens is difficult to observe clearly.
In the invention, the inductively coupled plasma emission spectrometry comprises the following specific steps:
1) shearing a sample, adding a digestion reagent, and placing the sample in a microwave digestion instrument for digestion, wherein the digestion procedure is as follows: heating to 140 ℃ for 15min, keeping for 10min, heating to 180 ℃ for 10min, keeping for 10min, heating to 200 ℃ for 10min, keeping for 5min, and fixing the volume to obtain a sample solution to be measured;
2) measuring a phosphorus element working curve solution by adopting an inductively coupled plasma emission spectrum, drawing a standard working curve, then measuring the concentration of phosphorus element in a sample solution to be measured, and when the concentration of the solution exceeds the highest point of the curve, diluting the sample solution to be measured and measuring again;
wherein the test conditions are as follows: the radio frequency power is 1300W, the observation direction is axial observation, the flow rate of the atomizer is 0.7L/min, the flow rate of the auxiliary gas is 0.2L/min, the flow rate of the plasma gas is 12L/min, the analysis pump speed is 1.0mL/min, and the analysis spectral line is 213.617 nm.
Under the test conditions, the standard solutions with different concentrations are analyzed, the detection limit (3 times of signal to noise ratio) of red phosphorus reaches 10ppm, the blank test result is less than the detection limit, and the test requirement of red phosphorus can be met.
In the present invention, the test conditions of the pyrolysis gas chromatography mass spectrometry are as follows:
the gas phase conditions were: a chromatographic column: DB-5 MS; temperature rising procedure: maintaining at 50 deg.C for 2min, increasing to 80 deg.C at a rate of 10 deg.C/min, maintaining for 1min, increasing to 310 deg.C at a rate of 15 deg.C/min, and maintaining for 5 min; sample inlet temperature: 300 ℃; sample introduction mode: the split ratio is 1: 100; carrier gas: helium with purity more than or equal to 99.999%; flow rate: 3 mL/min;
the mass spectrum parameters are as follows: ion source temperature: 230 ℃; interface temperature of chromatography-mass spectrometry: 250 ℃; an ionization mode: electron bombardment ionization; ionization energy: 70 eV; solvent delay time: 0.5 min; an acquisition mode: SCAN; SCAN mass SCAN range: 29-600 m/z, and carrying out qualitative analysis on the sample to be detected through a full SCAN mode SCAN;
the temperature of the cracker is 550-650 ℃.
The temperature of the cracker is lower than 550 ℃, and some high molecular materials with high decomposition temperature are difficult to crack, so that the red phosphorus is coated and not cracked easily, and the detection is missed; too high a cracking temperature tends to introduce more interfering impurities.
Example 1
(1) X-ray fluorescence spectroscopy
And (3) testing conditions are as follows: placing the standard into a special sample cup for XRF test, spreading the plastic sample on the bottom of the sample cup, and selecting a polymer qualitative method: the collimator is selected to be 10mm in the Polymer-Auto; analyzing the content of elements between Ti and U under the conditions of tube voltage of 50kV and tube current of 37 muA, and testing for 60 s; analyzing the content of elements between Al and Sc under the conditions of tube voltage of 50kV and tube current of 396 mu A, and testing for 60 s; and analyzing the content of elements between S and Ca under the conditions of tube voltage of 50kV and tube current of 676 mu A, and testing for 60S.
The element analysis result of the sample is shown in figure 2, the result shows that the sample may contain red phosphorus or other organic phosphorus substances, the verification needs to be carried out by combining microscopic image analysis, a pyrolysis gas chromatography-mass spectrometry combined method and ICP-OES, and the X fluorescence spectrum analysis can provide quantitative reference data for subsequent ICP-OES test in a semi-quantitative mode, so that repeated dilution of the sample is avoided.
If the element analysis result of the X fluorescence spectrometer shows that the sample does not contain phosphorus, the sample does not contain red phosphorus or other organic phosphorus, the ICP detection limit is only 10ppm, verification is carried out, subsequent microscopic image analysis, pyrolysis gas analysis and the like are not needed, the red phosphorus sample can be rapidly screened, and time and efficiency are saved for testing.
(2) Microscopic image analysis
A sample with a flat section of 2mm is cut out, the sample is placed in an electron microscope with the magnification adjusted to 800 times, the red phosphorus form in an eyepiece is observed, and a photograph of the observation is taken and recorded. It can be seen from fig. 3 that the sample has a distinct bright red spot, indicating that red phosphorus particles exist in the sample to be tested.
(3) Pyrolysis gas chromatography mass spectrometry
Qualitative analysis of a cracking gas chromatography mass spectrometer: 100 micrograms of standard were accurately weighed with a hundred thousand graded analytical balance and placed in a lysis cup.
Gas chromatography-mass spectrometer detector parameters:
the gas phase conditions were as follows:
a chromatographic column: DB-5MS (length 30m, film thickness 2.5 μm, inner diameter 0.25 mm); temperature rising procedure: initial 50 ℃ (hold for 2min), ramp up to 80 ℃ (hold for 1min) at 10 ℃/min, ramp up to 310 ℃ (hold for 5min) at 15 ℃/min injection port temperature: 300 ℃; sample introduction mode: the split ratio is 1: 100; carrier gas: helium with purity more than or equal to 99.999%; flow rate: 3 mL/min.
The mass spectrum parameters were as follows:
ion source temperature: 230 ℃; interface temperature of chromatography-mass spectrometry: 250 ℃; an ionization mode: electron bombardment ionization, ionization energy: 70 eV; solvent delay time: 0.5 min; an acquisition mode: SCAN; SCAN mass SCAN range (m/z): and 29-600, and performing qualitative determination on the substance to be detected through a full SCAN mode SCAN.
Temperature of the cracker:
the cracker temperature was chosen to be 600 ℃ based on the standard and the cracking conditions.
FIGS. 4 and 5 are the cracking gas chromatogram and the mass spectrogram of the red phosphorus standard substance, respectively; FIGS. 6 and 7 are the cracking gas chromatogram and mass spectrum of the positive sample, respectively. Comparing the spectra of the red phosphorus standard and the sample shows that the sample contains red phosphorus. Under the optimized gas chromatography-mass spectrometry analysis conditions, red phosphorus can be well separated within 14min, the peak shape is symmetrical, and the matrix interference is small.
(4) Quantitative analysis of phosphorus element by inductively coupled plasma emission spectrometry
1) Cutting the sample into pieces of 5mm by 5mm, weighing about 0.2g of the sample, accurately weighing to 0.0001g, adding digestion reagents such as nitric acid, hydrofluoric acid, hydrogen peroxide and the like, and placing the sample into a microwave digestion instrument for digestion. The digestion program is as follows: heating to 140 deg.C for 15min, maintaining for 10min, heating to 180 deg.C for 10min, heating to 200 deg.C for 10min, and maintaining for 5 min. After digestion, transferring the solution to a 50mL volumetric flask in a quantitative manner, and adding water to a constant volume;
2) and (3) testing the phosphorus element working curve solution by using ICP-OES, drawing a standard working curve, then testing the concentration of phosphorus element in the sample solution, and when the concentration of the solution exceeds the highest point of the curve, correspondingly diluting the solution and re-measuring, wherein the test conditions of the ICP-OES are shown in Table 1.
TABLE 1
Under the test conditions, the standard solutions with different concentrations are analyzed, the detection limit (3 times of signal to noise ratio) of red phosphorus reaches 10ppm, the blank test result is less than the detection limit, and the test requirement of red phosphorus can be met.
In conclusion, the invention adopts the combination of microscopic image analysis, pyrolysis gas chromatography-mass spectrometry and XRF and ICP-OES to determine the content of red phosphorus in the plastic product. The detection method can be used for rapidly, accurately and visually observing the red phosphorus particles in the plastic product, is simple in pretreatment method, avoids introducing unnecessary interference, can be used for more accurately eliminating the interference of other phosphorus-containing substances in the sample by combining with quantitative analysis of red phosphorus, and is high in detection efficiency and good in reproducibility.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A qualitative and quantitative detection method for red phosphorus in a plastic product is characterized by comprising the following steps:
(1) judging whether the sample contains phosphorus element or not through X fluorescence spectrum analysis;
(2) if the sample does not contain phosphorus, carrying out quantitative analysis on the phosphorus by using an inductively coupled plasma emission spectrometry; if the sample contains phosphorus elements, whether the sample contains red phosphorus particles is judged through microscopic image analysis;
(3) if the sample does not contain red phosphorus particles, carrying out quantitative analysis on phosphorus by adopting an inductively coupled plasma emission spectrometry; if the sample contains red phosphorus particles, the red phosphorus in the sample is qualitatively and quantitatively analyzed by adopting pyrolysis gas chromatography-mass spectrometry, and then the phosphorus element is quantitatively analyzed by adopting an over-inductive coupling plasma emission spectrometry.
2. The method for qualitatively and quantitatively detecting red phosphorus in plastic products as claimed in claim 1, wherein the test conditions of the X-fluorescence spectroscopic analysis are as follows: the collimator is 10 mm; analyzing the content of elements between Ti and U under the conditions of tube voltage of 50kV and tube current of 37 muA, and testing for 60 s; analyzing the content of elements between Al and Sc under the conditions of tube voltage of 50kV and tube current of 396 mu A, and testing for 60 s; analyzing the content of elements between S and Ca under the conditions of tube voltage of 50kV and tube current of 676 mu A, and testing for 60S; and a vacuum pumping mode is adopted.
3. The method as claimed in claim 1, wherein the magnification in the analysis of the microscope image is 800-1000 times.
4. The method for qualitatively and quantitatively detecting red phosphorus in plastic products as claimed in claim 1, wherein the inductively coupled plasma emission spectrometry comprises the following specific steps:
1) shearing a sample, adding a digestion reagent, and placing the sample in a microwave digestion instrument for digestion, wherein the digestion procedure is as follows: heating to 100-160 ℃ for 5-15 min, keeping for 10-15 min, heating to 160-200 ℃ for 10min, keeping for 10min, heating to 200-240 ℃ for 10min, keeping for 5min, and fixing the volume to obtain a sample solution to be measured;
2) measuring a phosphorus element working curve solution by using an inductively coupled plasma emission spectrometer, drawing a standard working curve, then measuring the concentration of phosphorus element in a sample solution to be measured, and when the concentration of the solution exceeds the highest point of the curve, diluting the sample solution to be measured and measuring again;
wherein the test conditions are as follows: the radio frequency power is 1300W, the observation direction is axial observation, the flow rate of the atomizer is 0.5-0.7L/min, the auxiliary gas flow rate is 0.2L/min, the plasma gas flow rate is 12L/min, the analysis pump speed is 1.0mL/min, and the analysis spectral line is 213.617 nm.
5. The method for qualitatively and quantitatively detecting red phosphorus in plastic products as claimed in claim 1, wherein the test conditions of the pyrolysis gas chromatography mass spectrometry are as follows:
the gas phase conditions were: a chromatographic column: DB-5 MS; temperature rising procedure: maintaining at 50 deg.C for 2min, increasing to 80 deg.C at a rate of 10 deg.C/min, maintaining for 1min, increasing to 310 deg.C at a rate of 15 deg.C/min, and maintaining for 5 min; sample inlet temperature: 300 ℃; sample introduction mode: the split ratio is 1: 100; carrier gas: helium with purity more than or equal to 99.999%; flow rate: 3 mL/min;
the mass spectrum parameters are as follows: ion source temperature: 230 ℃; interface temperature of chromatography-mass spectrometry: 250 ℃; an ionization mode: electron bombardment ionization; ionization energy: 70 eV; solvent delay time: 0.5 min; an acquisition mode: SCAN; SCAN mass SCAN range: 29-600 m/z;
the temperature of the cracker is 550-650 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115684459A (en) * | 2022-10-27 | 2023-02-03 | 云南云天化股份有限公司 | Method for determining total phosphorus in polyphosphate polymer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995112A (en) * | 2006-12-26 | 2007-07-11 | 温州大学 | Preparation method of microcapsuled red phosphorus for polyurethane resin |
| CN101498694A (en) * | 2009-03-02 | 2009-08-05 | 谱尼测试科技（北京）有限公司 | Method for measuring red phosphorus content in electronic materials |
| CN102507476A (en) * | 2011-11-10 | 2012-06-20 | 天祥（广州）技术服务有限公司 | Method for measuring cadmium in plastic sample |
| CN102507299A (en) * | 2011-11-02 | 2012-06-20 | 苏州华碧微科检测技术有限公司 | Pretreatment method for detecting elements of polyvinyl chloride plastics |
| CN102564973A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for quickly measuring content of phosphorus, lead and zinc in industrial ferrous dust |
| CN103293144A (en) * | 2013-06-26 | 2013-09-11 | 天津虹炎科技有限公司 | ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) measurement of content of impurity phosphorus in steel |
| CN106053431A (en) * | 2016-08-12 | 2016-10-26 | 广西壮族自治区分析测试研究中心 | ICP-AES determination method for contents of phosphorus and sulfur in plant |
| CN107024557A (en) * | 2016-01-29 | 2017-08-08 | 深圳市虹彩检测技术有限公司 | The assay method of red phosphorus content and application |
| CN110261504A (en) * | 2019-06-21 | 2019-09-20 | 广东省微生物研究所（广东省微生物分析检测中心） | A method of with red phosphorus content in thermal cracking gas chromatography-mass spectral analysis sample |
-
2019
- 2019-11-28 CN CN201911193544.3A patent/CN110806474A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995112A (en) * | 2006-12-26 | 2007-07-11 | 温州大学 | Preparation method of microcapsuled red phosphorus for polyurethane resin |
| CN101498694A (en) * | 2009-03-02 | 2009-08-05 | 谱尼测试科技（北京）有限公司 | Method for measuring red phosphorus content in electronic materials |
| CN102564973A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for quickly measuring content of phosphorus, lead and zinc in industrial ferrous dust |
| CN102507299A (en) * | 2011-11-02 | 2012-06-20 | 苏州华碧微科检测技术有限公司 | Pretreatment method for detecting elements of polyvinyl chloride plastics |
| CN102507476A (en) * | 2011-11-10 | 2012-06-20 | 天祥（广州）技术服务有限公司 | Method for measuring cadmium in plastic sample |
| CN103293144A (en) * | 2013-06-26 | 2013-09-11 | 天津虹炎科技有限公司 | ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) measurement of content of impurity phosphorus in steel |
| CN107024557A (en) * | 2016-01-29 | 2017-08-08 | 深圳市虹彩检测技术有限公司 | The assay method of red phosphorus content and application |
| CN106053431A (en) * | 2016-08-12 | 2016-10-26 | 广西壮族自治区分析测试研究中心 | ICP-AES determination method for contents of phosphorus and sulfur in plant |
| CN110261504A (en) * | 2019-06-21 | 2019-09-20 | 广东省微生物研究所（广东省微生物分析检测中心） | A method of with red phosphorus content in thermal cracking gas chromatography-mass spectral analysis sample |
Non-Patent Citations (6)
| Title |
|---|
| 张智: "塑胶材料阻燃剂红磷的定性定量分析方法研究", 《化工管理》 * |
| 杨明等: "微波消解样品-电感耦合等离子体原子发射光谱法测定阻燃纤维材料中微量磷", 《理化检验(化学分册)》 * |
| 桑洁等: "MQ硅树脂微胶囊红磷阻燃剂的制备工艺研究", 《磷肥与复肥》 * |
| 胡生平: "微波消解-电感耦合等离子体原子发射光谱法测定塑料中P元素", 《塑料工业》 * |
| 金献忠;朱丽辉;陈建国;黄本立;: "塑料制品中铅、汞、镉、铬(Ⅵ)测定" * |
| 高俊海等: "红磷阻燃剂的检测方法研究进展", 《现代科学仪器》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115684459A (en) * | 2022-10-27 | 2023-02-03 | 云南云天化股份有限公司 | Method for determining total phosphorus in polyphosphate polymer |
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