WO2022269763A1 - Method for measuring phthalic-acid-ester- and bromine-based flame-retardant compound, and gas chromatography for use in said method - Google Patents
Method for measuring phthalic-acid-ester- and bromine-based flame-retardant compound, and gas chromatography for use in said method Download PDFInfo
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- WO2022269763A1 WO2022269763A1 PCT/JP2021/023636 JP2021023636W WO2022269763A1 WO 2022269763 A1 WO2022269763 A1 WO 2022269763A1 JP 2021023636 W JP2021023636 W JP 2021023636W WO 2022269763 A1 WO2022269763 A1 WO 2022269763A1
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- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000003063 flame retardant Substances 0.000 title abstract description 9
- -1 flame-retardant compound Chemical class 0.000 title abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title abstract 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052794 bromium Inorganic materials 0.000 title abstract 2
- 238000004817 gas chromatography Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 205
- 238000000926 separation method Methods 0.000 claims abstract description 104
- 238000004458 analytical method Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 125000006267 biphenyl group Chemical class 0.000 claims abstract description 7
- 125000005498 phthalate group Chemical class 0.000 claims description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 31
- 230000005526 G1 to G0 transition Effects 0.000 claims description 27
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 11
- 230000008016 vaporization Effects 0.000 abstract description 13
- 235000010290 biphenyl Nutrition 0.000 abstract description 6
- 150000004074 biphenyls Chemical class 0.000 abstract description 6
- 150000003021 phthalic acid derivatives Chemical class 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 62
- 230000001105 regulatory effect Effects 0.000 description 56
- 150000002500 ions Chemical class 0.000 description 49
- 239000011347 resin Substances 0.000 description 34
- 229920005989 resin Polymers 0.000 description 34
- 230000004044 response Effects 0.000 description 25
- 238000012216 screening Methods 0.000 description 25
- 239000007789 gas Substances 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 21
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 20
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 18
- 239000012159 carrier gas Substances 0.000 description 18
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 18
- 238000011002 quantification Methods 0.000 description 15
- 238000011088 calibration curve Methods 0.000 description 14
- 239000000356 contaminant Substances 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 8
- 238000012790 confirmation Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000002098 selective ion monitoring Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000009 pyrolysis mass spectrometry Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/12—Preparation by evaporation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Definitions
- the present invention relates to a method for measuring phthalate esters and brominated flame retardant compounds, and a gas chromatograph column used in carrying out the method.
- Phthalates di(2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP)
- PBBs polybrominated biphenyls
- PBDEs polybrominated diphenyl ethers
- Pyrolysis-gas chromatography/mass spectrometry and pyrolyzer/thermal desorption-gas chromatography/mass spectrometry (Py-GC/MS) are used to measure phthalates, PBBs, and PBDEs in resin samples.
- /TD-GC/MS method is used.
- a container containing a resin sample is introduced into a pyrolyzer and heated to thermally decompose the resin.
- PBDEs hereinafter collectively referred to as "regulated compounds" are introduced into the gas chromatograph.
- the resin sample is heated, for example, to about 600°C.
- a container containing a resin sample is introduced into a pyrolyzer and heated to a temperature below the temperature at which the resin thermally decomposes, thereby desorbing the regulated compounds contained in the resin from the resin. to the gas chromatograph.
- the resin sample is heated, for example, to about 340°C.
- Non-Patent Document 1 describes that an insert tube is used to attach a guard column to a separation column in the following procedure. First, the guard column is inserted from one end of the insert tube, and the separation column is inserted from the other end. A ferrule is then placed on each end of the insert tube. Finally, the guard column and the separation column positioned inside the insert tube are fixed by attaching nuts to the outside of the ferrules positioned at both ends and crushing the ferrules.
- connecting the guard column described in Non-Patent Document 1 to the separation column requires a three-step work process, which takes time and effort.
- the connection between the guard column and the separation column is not perfect, carrier gas and regulated compounds will leak, resulting in erroneous measurement results.
- Non-Patent Document 1 a metal insert tube is used.
- the regulated compounds include those that are highly reactive with metals, and there is a gap between the guard column inserted in the insert tube and the separation column. Then, if a highly reactive regulated compound is adsorbed on the metal constituting the insert tube and then decomposed, the content of the regulated compound cannot be measured correctly.
- the problem to be solved by the present invention is that it is possible to suppress the deterioration of the separation column without requiring complicated work, and to accurately measure phthalates and brominated flame retardants that are easily adsorbed and decomposed. To provide a method and a gas chromatographic column for use in carrying out the method.
- the method for measuring phthalate esters and brominated flame retardant compounds according to the present invention which has been made to solve the above problems, heating a sample containing a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group to vaporize the target compound contained in the sample;
- An analysis column having a separation column internally provided with a stationary phase for separating the target compound, and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts. , adjusting the temperature to a temperature lower than the maximum temperature at which the target compound is vaporized, introducing the vaporized target compound into the analysis column; A target compound flowing out from the separation column is detected.
- Another aspect of the present invention which has been made to solve the above problems, is a gas chromatograph column used in carrying out a method for measuring phthalates and brominated flame retardant compounds, a separation column provided with a stationary phase for separating a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group; and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts.
- a column provided with a stationary phase for separating target compounds belonging to at least one of phthalates, polybrominated biphenyls, and polybrominated diphenyl ethers, and a An analysis column having the separation column and a guard column provided integrally is used.
- the separation column and the guard column are integrally constructed without using connecting parts, there is no need to connect them, and the carrier gas or the target compound leaks from the connection between the two.
- the target compound is not adsorbed to the connecting member and decomposed. Therefore, deterioration of the separation column can be suppressed without requiring complicated work, and phthalate esters and brominated flame-retardant compounds, which tend to adhere to the separation column or decompose, can be measured correctly.
- FIG. 4 is a diagram showing the configuration of a column in this embodiment; Graph showing the relationship between the length of the guard column and the flow rate of the carrier gas when the flow rate of the carrier gas is constant. Measurement conditions for phthalate esters and brominated flame retardant compounds in this example.
- An example of a relative sensitivity coefficient table in this embodiment. 1 is a flow chart showing a procedure in an embodiment of a method for measuring phthalates and brominated flame retardants according to the present invention.
- FIG. 4 is a flow chart showing the procedure in another example of the method for measuring phthalate esters and brominated flame retardant compounds according to the present invention. Measurement results confirming the effects of the measurement method and the chromatographic column for the phthalate esters and brominated flame retardant compounds of this example.
- FIG. 1 shows the main configuration of a pyrolyzer-gas chromatograph/mass spectrometer (Py-GC-MS) 1 used in the method for measuring a regulated compound in this example.
- the Py-GC-MS 1 is roughly divided into a gas chromatograph section 10, a mass spectrometry section 20, and a control/processing section 30.
- the gas chromatograph unit 10 includes a sample vaporization chamber 11, a pyrolyzer 12 provided in the sample vaporization chamber 11, a carrier gas flow path 13 connected to the sample vaporization chamber, and an outlet of the sample vaporization chamber 11.
- a column 14 is provided. Column 14 is housed inside column oven 15 .
- the pyrolyzer 12 and the column 14 in the column oven 15 are each heated to a predetermined temperature by a heating mechanism (not shown).
- FIG. 2 shows the structure of the column 14 (corresponding to the analysis column in the present invention) used in this example.
- Column 14 is composed of guard column 141 and separation column 142 .
- the guard column 141 is provided seamlessly and integrally with the separation column 142 on the side of the sample injection port of the separation column 142 .
- Both the guard column 141 and the separation column 142 are capillary tubes made of fused silica with an inner diameter of 0.25 mm. liquid phase) is provided.
- 100% dimethylpolysiloxane with a film thickness of 0.1 ⁇ m is used as the stationary phase.
- a stationary phase other than dimethylpolysiloxane may be used to measure the controlled compound.
- the regulated compound in this example is a highly polar compound
- the film thickness is preferably 0.05 ⁇ m or more because it is necessary to desorb from the stationary phase by generating a certain degree of interaction with each regulatory compound.
- guard columns have a stationary phase inside.
- contaminants are more likely to be collected and less likely to reach the separation column, so that the separation column is less likely to be contaminated.
- both contaminants and the target compound are collected on the stationary phase of the guard column, so peak tailing is likely to occur when measuring the target compound.
- a guard column 141 without a stationary phase is used in order to prevent tailing of the peak of the regulated compound.
- the length of the guard column 141 of this embodiment is 2 m, and the length of the separation column 142 is 15 m.
- the guard column 141 is used to prevent the separation column 142 from being contaminated by substances other than the regulated compounds (resin thermal decomposition products, contaminant compounds, etc.) released when the resin sample is heated by the pyrolyzer 12. . Since the temperature at which the column 14 is heated by the column oven 15 is lower than the temperature at which the pyrolyzer 12 is heated, these substances released from the pyrolyzer 12 are gradually cooled and adhere to the inner wall surface of the guard column 141 . If guard column 141 is shorter than 50 cm, these substances can easily enter separation column 142 .
- the length of the guard column 141 is preferably 50 cm or more and 4 m or less.
- FIG. 3 shows the relationship between the carrier gas flow rate and the length of the guard column required to achieve a linear velocity of 52.1 cm/sec using the same separation column with a length of 15 m and an inner diameter of 0.25 mm as in this example. .
- the length of the guard column 141 is 4 m or less, the increase in the carrier gas flow rate can be suppressed to 30% or less of the flow rate when the guard column 141 is not used.
- the guard column 141 with a length of 2 m is used as in the present embodiment, the linear velocity can be the same as when the guard column 141 is not used, simply by increasing the flow rate of the carrier gas by 10%.
- the flow rate of the carrier gas itself depends on the inner diameter of the column and the length of the separation column, but in many cases, the relationship between the flow rate of the carrier gas and the length of the guard column is similar to that shown in FIG. Therefore, it is preferable to set the length of the guard column to 50 cm or more and 4 m or less.
- the mass spectrometer 20 includes an electron ionization source 22 , an ion lens 23 , a quadrupole mass filter 24 and an ion detector 25 inside a vacuum chamber 21 .
- Sample components temporally separated inside the column 14 are sequentially introduced into the electron ionization source 22 and ionized by irradiation with thermal electrons emitted from a filament (not shown).
- the control/processing unit 30 has a storage unit 31 .
- the storage unit 31 stores method files used when measuring the controlled compounds.
- a method file is a file that describes measurement conditions for a regulated compound.
- the measurement conditions include the temperature of the pyrolyzer 12, the temperature of the separation column 142 (the temperature of the column oven 15), the type and flow rate of the carrier gas, and the phthalates, PBBs, and PBDEs, which are regulated compounds. It contains information such as two types of ions (a quantifying ion and a confirming ion).
- FIG. 4 shows an example of measurement conditions.
- Figure 4 shows three ions for phthalates (one quantifying ion and two confirming ions) and two ions for PBBs and PBDEs (one quantifying ion and one confirming ion). ) is described.
- a quantifying ion is used to quantify the compound from the area (or height) of the peak of the quantifying ion.
- the confirmation ion is used to confirm (identify) the compound based on the fact that the ratio of the height of the peak area of the quantitation ion and the height of the peak area of the confirmation ion is within a preset range.
- the storage unit 31 also stores information on the mass-to-charge ratio of one or more preliminary ions for each compound.
- the storage unit 31 stores a relative response coefficient database 311 .
- the relative response factor database 311 associates one or more predetermined reference compounds included in the regulated compounds with reference compounds that are regulated compounds other than the reference compounds.
- the ratio of the detection sensitivity of the reference compound to the detection sensitivity of the reference compound (relative response factor RRF) is stored in a database.
- RRF relative response factor
- An example of a relative response factor table for PBBs and PBDEs is shown in FIG.
- a relative response coefficient database (for example, Non-Patent Document 4) is stored for phthalates.
- the relative response factor database 311 is used when performing "2-1. Screening of regulated compounds using the relative response factor database" (described later), and "2-2. When “screening of regulated compounds” (described later) is performed, it is not necessary to store the relative response coefficient database 311 in the storage unit 31.
- FIG. 1 Screening of regulated compounds using the relative response factor database
- RRF a/x The relative response factor RRF a/x of the reference compound a with respect to the standard compound x is represented by the following formula (1).
- RRFa /x RFa / RFx ...(1) where RFa and RFx are the response factors for reference compound a and reference compound x, respectively.
- the control/processing unit 30 includes, as functional blocks, a reference compound determination unit 32, a standard sample measurement unit 33, an analysis target sample measurement unit 34, a reference compound quantification unit 35, a reference compound quantification unit 36, and a screening unit 37. .
- the entity of the control/processing unit 30 is a general personal computer, and each functional block described above is realized by executing a preinstalled analysis sample measurement program on the processor.
- the control/processing unit 30 is also connected to an input unit 4 for a user to perform an input operation and a display unit 5 for displaying various information.
- the reference compound determination unit 32 and the reference compound quantification unit 36 (the functional blocks indicated by the dashed lines in FIG. 1) perform “2-1.
- control/processing unit 30 controls the standard sample measurement unit 33, the analysis target A sample measurement unit 34, a reference compound quantification unit (quantification unit) 35, and a screening unit 37 (functional blocks indicated by solid lines in FIG. 1) may be provided.
- the Py-GC-MS1 of this embodiment can perform two types of screening, ie, screening of controlled compounds using a relative response coefficient database and screening of controlled compounds using a calibration curve for each controlled compound.
- the reference compound determination unit 32 reads the relative response coefficient database 311 from the storage unit 31 and displays the relative response coefficient table (FIG. 5) described therein on the display unit 5. do.
- the user confirms this and changes the correspondence between the standard compound and the reference compound if necessary. For example, if it is difficult to obtain a standard sample containing the reference compound selected in the relative response coefficient table, the compound may be deleted from the reference compound, or another compound may be set as the reference compound. can be done.
- the reference compound is determined (step 1).
- the standard sample measurement unit 33 performs measurement conditions described in the method file associated with the relative response coefficient database 311 stored in the storage unit 31 (related to measurement of the reference compound). (Step 2).
- the temperature of the pyrolyzer 12 is first raised from 200° C. at a rate of 20° C./min based on the measurement conditions shown in FIG. After reaching 300° C., the temperature is raised at a rate of 5° C./min, and when the temperature reaches 340° C., the temperature is maintained for 1 minute.
- the controlled compound contained in the standard sample is vaporized (step 21).
- the vaporized controlled compound is introduced into the analysis column 14 along with the carrier gas flow.
- the standard sample measurement unit 33 displays the completion of heating on the display unit 5 (or notifies by voice or the like) and instructs the user to take out the container.
- each substance including the decomposed resin vaporized from the standard sample by the pyrolyzer 12 is introduced into the analysis column 14 while being gradually cooled (step 23).
- Decomposed resin introduced into the analysis column 14 adheres to the inner wall inside the guard column 141 provided on the inlet side of the analysis column 14 .
- the regulated compound adheres to the inner wall of the guard column 141 or mainly reaches the inlet of the separation column 142 and adheres.
- the standard sample measuring section 33 starts heating the column oven 15 .
- the temperature was raised from 80° C. at a rate of 20° C./min and maintained at 320° C. for 4 minutes.
- the regulated compounds adhering to the inlet of the separation column 142 enter the separation column 142 in order from those that have reached the vaporization temperature of each compound, and are transferred to the stationary phase 1421 by the action of the stationary phase 1421 of the separation column 142. It advances through the separation column 142 while desorbing and flows out. Compounds exiting the separation column 142 are in turn introduced into the electron ionization source 22 .
- the ions generated by the electron ionization source 22 are converged near the central axis (ion optical axis C) in the direction of flight by the ion lens 23, and then enter the quadrupole mass filter 24. It is separated and detected by the ion detector 25 (step 24). Output signals from the ion detector 25 are sequentially transmitted to and stored in the storage unit 31 .
- the mass spectrometry unit 20 repeatedly performs scan measurement and selective ion monitoring (SIM) measurement. Specifically, the mass-to-charge ratio of ions passing through the quadrupole mass filter 24 is scanned in a predetermined range (for example, the range of m/z is 50 to 1000), and A preset SIM measurement for each m/z in which the mass-to-charge ratio of the ion to be measured is fixed to the mass-to-charge ratio of the quantitation ion or confirming ion of each compound for a predetermined time is set as one set, and this is repeated. Note that the scan measurement is not essential, and only the SIM measurement may be repeatedly performed.
- SIM selective ion monitoring
- n-alkane samples are also measured.
- An n-alkane sample is a standard sample containing multiple compounds with different hydrocarbon chain lengths, and is used to obtain a retention index based on the retention time of each compound.
- the retention index Ix of compound x is represented by the following formula (4).
- C n , C n+i are the numbers of carbon atoms in n-alkanes positioned before and after the retention time of the compound
- t x is the retention time of compound x
- t n , t n+i are the retention times of the n-alkanes before and after the retention time of the compound.
- the standard sample measuring section 33 Upon completion of the measurement of the standard sample, the standard sample measuring section 33 creates a calibration curve corresponding to each reference compound (step 3). Here, only one standard sample is measured to create a one-point calibration curve. When the amount of the reference compound and the measured intensity are in a non-linear relationship, a plurality of standard samples with different contents of the reference compound may be measured to create a calibration curve based on two or more measurement points.
- the user After creating the calibration curve of the reference compound, the user sets the sample to be analyzed and instructs the start of measurement.
- the sample to be analyzed is measured using the measurement conditions obtained (step 4). Specifically, based on the measurement conditions shown in FIG. 3, the pyrolyzer 12 is first heated from 200° C. at a rate of 20° C./min. After reaching 300° C., the temperature is raised at a rate of 5° C./min, and when the temperature reaches 340° C., the temperature is maintained for 1 minute. As a result, the controlled compound contained in the standard sample is vaporized (step 41). The vaporized controlled compound is introduced into the analysis column 14 along with the carrier gas flow.
- the standard sample measurement unit 33 displays the completion of heating on the display unit 5 (or notifies by voice or the like) and instructs the user to take out the container.
- each substance including the decomposed resin vaporized from the sample to be analyzed by the pyrolyzer 12 is introduced into the analysis column 14 while being gradually cooled (step 43).
- Decomposed resin products introduced into the analysis column 14 adhere to the inner wall of the guard column 141 provided on the inlet side of the analysis column 14 .
- the regulated compound adheres to the inner wall of the guard column 141 or mainly reaches the inlet of the separation column 142 and adheres.
- the standard sample measuring section 33 starts heating the column oven 15 .
- the temperature was raised from 80° C. at a rate of 20° C./min and maintained at 320° C. for 4 minutes.
- the regulated compounds adhering to the inlet of the guard column 141 or the separation column 142 enter the separation column 142 in order from those that have reached the vaporization temperature of each compound, and interact with the stationary phase 1421 of the separation column 142. It advances through the separation column 142 while desorbing to the stationary phase 1421 and flows out.
- the compounds discharged from the separation column 142 are sequentially mass-separated by the mass spectrometer 20 and detected by the ion detector 25 (step 44).
- an n-alkane sample may also be measured separately from the measurement of the sample to be analyzed.
- scan measurement is not essential, and only SIM measurement may be performed.
- by performing scan measurement if a large peak other than the compound to be measured is found after creating the total ion current chromatogram, by analyzing the mass spectrum obtained at the retention time of the peak, Compounds corresponding to peaks can be identified.
- the reference compound quantification unit 35 When the measurement of the sample to be analyzed is completed, the reference compound quantification unit 35 generates quantitative ions and confirmation ions based on the respective retention indices of the reference compounds, or the predicted retention times calculated based on the retention indices and the measurement data of n-alkanes. Determine the mass chromatogram peak of . Then, it is confirmed that the peak area of the quantitative ion and the peak area of the confirmation ion are within a predetermined range, and the quantitative value is obtained by comparing the peak area of the quantitative ion with the calibration curve of the reference compound (step 5). .
- the reference compound quantification unit 36 calculates the retention time of each reference compound, or the predicted retention time calculated based on the retention index of each reference compound and the measurement data of n-alkane, Determine the mass chromatogram peaks of the quantitation and confirming ions for each reference compound. Then, it is confirmed that the peak area of the quantitative ions and the peak area of the confirmation ions are within a predetermined range.
- quantitation of each reference compound based on the amount of the reference compound contained in the standard sample, the peak area of the quantification ion of the reference compound detected by measuring the standard sample, the peak area of the quantification ion of the reference compound and the relative response factor Obtain a value (step 6).
- the screening unit 37 compares these quantitative values with predetermined threshold values to screen the sample to be analyzed.
- predetermined threshold values the amount of DEHP, the amount of BBP, the amount of DBP, the amount of DIBP, the total amount of PBBs, and the total amount of PBDEs are all 1000 mg / kg or less
- the analysis target Screening judgment whether the quantitative values of DEHP, BBP, DBP, and DIBP contained in the sample are within the range of ⁇ 50% of the reference value, and whether the total amount of PBBs and PBDEs is within the range of ⁇ 70% of the reference value. (step 7).
- Non-Patent Document 5 the following criteria described in Non-Patent Document 5 can be used. If the quantitative value of DEHP, BBP, DBP, and DIBP contained in the sample to be analyzed is 500 mg/kg or less, and if the total quantitative value of PBBs and PBDEs is all 300 mg/kg or less, the analysis Judge that the target sample satisfies the standards of the RoHS Directive. In addition, if the quantitative values of DEHP, BBP, DBP, and DIBP are 1500mg/kg or more, or if any of the total quantitative values of PBBs and PBDEs is 1700mg/kg or more, the sample to be analyzed shall comply with the RoHS Directive. judged not to meet the criteria.
- the standard sample measurement unit 33 When the user sets a container containing a standard sample, which is a resin sample containing known amounts of all regulated compounds, to the pyrolyzer and instructs the start of measurement, the standard sample measurement unit 33 is stored in the storage unit 31.
- the standard sample is measured according to the measurement conditions described in the method file (step 11).
- the procedure (steps 21 to 24) for the measurement of the standard sample is the same as in the case of using the relative response factor database (except that all controlled compounds are measured), so a detailed explanation is omitted.
- the standard sample measurement unit 33 After completing the measurement of the standard sample, the standard sample measurement unit 33 creates a calibration curve for each regulated compound (step 12). Again, measure only one standard sample to create a one-point calibration curve. If there is a non-linear relationship between the amount of a regulated compound and the measured intensity, multiple standard samples with different contents of the regulated compound may be measured, and a calibration curve based on two or more measurement points may be created.
- the user After creating the calibration curve for each regulated compound, the user sets the sample to be analyzed and instructs the start of measurement.
- the sample to be analyzed is measured using the measurement conditions described in the method file (step 13).
- the procedure (steps 41 to 44) for measurement of the sample to be analyzed is also the same as in the case of using the relative response coefficient database, so detailed description will be omitted.
- the reference compound quantification unit 35 determines the mass chromatogram peaks of the quantitative ions and confirmation ions of each regulated compound based on the retention time of each regulated compound obtained during the measurement of the standard sample. to decide. Then, it is confirmed that the peak area of the quantitative ion and the peak area of the confirmation ion are within a predetermined range, and the quantitative value is obtained by comparing the peak area of the quantitative ion with the calibration curve of each regulatory compound (step 14). .
- the screening unit 37 compares these quantitative values with predetermined threshold values to screen the sample to be analyzed.
- analysis based on the standard values in the RoHS Directive (the amount of DEHP, the amount of BBP, the amount of DBP, the amount of DIBP, the total amount of PBBs, and the total amount of PBDEs are all 1000 mg/kg or less). Screening whether the quantified values of DEHP, BBP, DBP, and DIBP contained in the target sample are within ⁇ 50% of the standard value, and whether the total amount of PBBs and PBDEs are within ⁇ 70% of the standard value. Determine (step 15).
- the separation column 142 provided with the stationary phase for separating the controlled compound and the guard column 141 provided integrally with the separation column 142 on the inlet side of the separation column 142 are used.
- the carrier gas and the regulated compound do not leak from the connection between the two, and the regulated compound does not adsorb and decompose when the connecting member is touched. Therefore, deterioration of the separation column 142 can be suppressed without requiring complicated work, and regulated compounds that tend to adhere to the separation column 142 or decompose can be measured correctly.
- FIG. 8 shows the results of measurement using the column 14 of the above example (measurement conditions are the same as in the above example in FIG. 4).
- the graph in FIG. 8 plots changes in the symmetry coefficient with respect to the number of measurements.
- a column without a guard column usually had a symmetry coefficient of more than 2.5 after 300-400 measurements. .
- the above embodiment is just an example, and can be modified as appropriate in line with the spirit of the present invention.
- Py-GC-MS1 was used to thermally desorb the controlled compound by the Py/TD-GC/MS method to screen the sample for analysis. It is also possible to screen the sample to be analyzed by
- the apparatus configuration for the Py-GC/MS method is the same as in the above examples, and the sample heating temperature by the pyrolyzer is different.
- the maximum temperature at which the resin sample is heated in order to vaporize the target compound contained in the resin sample is higher than the heating temperature of the separation column. Since other substances (decomposition products of the resin and contaminant compounds) are introduced into the analysis column 14, contamination of the separation column 142 can be prevented by providing the guard column 141 as in the above embodiment.
- the guard column 141 and the separation column 142 are integrally configured without connecting fittings such as nuts and ferrules, compounds that easily adsorb and decompose, such as phthalates and flame-retardant brominated compounds, are not used. can be measured correctly.
- each compound flowing out from the column 14 was configured to be subjected to mass spectrometry, but each compound can also be detected by a method other than mass spectrometry.
- detectors include, for example, flame ionization detectors (FID), thermal ionization detectors (FTD), flame photometric detectors (FPD), electron capture detectors (ECD), sulfur chemiluminescence detectors (SCD). , thermal conductivity detector (TCD), barrier discharge ionization detector (BID), etc. can also be used.
- a method for measuring a phthalate ester and a brominated flame retardant compound comprises: heating a sample containing a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group to vaporize the target compound contained in the sample; An analysis column having a separation column internally provided with a stationary phase for separating the target compound, and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts. , adjusting the temperature to a temperature lower than the maximum temperature at which the target compound is vaporized, introducing the vaporized target compound into the analysis column; A target compound flowing out from the separation column is detected.
- FIG. 8 Another aspect of the present invention is a gas chromatograph column used in carrying out a method for measuring phthalates and brominated flame retardant compounds, a separation column provided with a stationary phase for separating a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group; and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts.
- the gas chromatograph column described in Section 8 is used in the method for measuring phthalates and brominated flame retardant compounds in Section 1.
- the separation column and the guard column are integrally constructed without using connecting parts, so there is no need to connect them.
- the target compound is not adsorbed and decomposed. Therefore, deterioration of the separation column can be suppressed without requiring complicated work, and phthalate esters and brominated flame-retardant compounds, which tend to adhere to the separation column or decompose, can be measured correctly.
- the target compound is vaporized by thermal decomposition and the target by thermal desorption.
- the method of vaporizing the compound can be properly used.
- guard columns have a stationary phase (liquid phase) inside.
- a stationary phase liquid phase
- contaminants are more likely to be collected and less likely to reach the separation column, so that the separation column is less likely to be contaminated.
- contaminants trapped in the stationary phase of the guard column flow out, and the peak tends to tail when the target compound is measured.
- an analysis column in which a stationary phase is provided only in the separation column is used. Content can be measured accurately.
- the guard column has a length of 50 cm or more and 4 m or less.
- the use of a guard column with a length of 50 cm or longer causes contaminants such as resin decomposition products to enter the separation column and contaminate the separation column. can be prevented.
- the guard column is 4 m or shorter, the target compound can be measured at the same linear velocity by increasing the flow rate of the carrier gas by about 30% compared to when the guard column is not used.
- the separation column has a length of 10 m or more and 30 m or less.
- the controlled compounds contained in the sample can be sufficiently separated by using a separation column with a length of 10m or longer. Moreover, since the length of the separation column is 30 m or less, the measurement time does not become extremely long.
- Resin samples containing phthalates and brominated flame retardant compounds contain various contaminants other than the target compound.
- decomposition products of the resin also enter the column of the gas chromatograph when the target compound is vaporized.
- each compound that has flowed out from the separation column is detected by mass separation, so even if contaminants co-eluted with the target compound are present, Contaminants can be found with high accuracy and the content of target compounds can be measured correctly.
- the method for measuring the phthalate esters and brominated flame retardant compounds described in items 1 to 6 is as described in item 7. Whether the content of the target compound is within a predetermined range or not It can be suitably used for screening the sample based on the above. In particular, by using an analysis column having a guard column and a separation column having lengths as described in the fourth and fifth items, the sample to be analyzed can be screened with high efficiency.
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Abstract
Description
フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を含有する試料を加熱して該試料に含まれる対象化合物を気化させ、
内部に前記対象化合物を分離するための固定相が設けられた分離カラムと、接続部品を用いることなく該分離カラムの入口側に該分離カラムと一体に設けられたガードカラムとを有する分析カラムを、前記対象化合物を気化させる際の最高温度よりも低い温度に温調し、
気化させた前記対象化合物を前記分析カラムに導入し、
前記分離カラムから流出する対象化合物を検出する
ものである。 The method for measuring phthalate esters and brominated flame retardant compounds according to the present invention, which has been made to solve the above problems,
heating a sample containing a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group to vaporize the target compound contained in the sample;
An analysis column having a separation column internally provided with a stationary phase for separating the target compound, and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts. , adjusting the temperature to a temperature lower than the maximum temperature at which the target compound is vaporized,
introducing the vaporized target compound into the analysis column;
A target compound flowing out from the separation column is detected.
フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を分離するための固定相が設けられた分離カラムと、
接続部品を用いることなく前記分離カラムの入口側に該分離カラムと一体に設けられたガードカラムと
を備える。 Another aspect of the present invention, which has been made to solve the above problems, is a gas chromatograph column used in carrying out a method for measuring phthalates and brominated flame retardant compounds,
a separation column provided with a stationary phase for separating a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group;
and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts.
図1に、本実施例の規制化合物の測定方法において使用する、パイロライザー-ガスクロマトグラフィ/質量分析装置(Py-GC-MS)1の要部構成を示す。 1. Configuration of Py-GC-MS FIG. 1 shows the main configuration of a pyrolyzer-gas chromatograph/mass spectrometer (Py-GC-MS) 1 used in the method for measuring a regulated compound in this example.
RRFa/x=RFa/RFx …(1)
ここで、RFaとRFxはそれぞれ、参照化合物aと基準化合物xの応答係数である。 The relative response factor RRF a/x of the reference compound a with respect to the standard compound x is represented by the following formula (1).
RRFa /x = RFa / RFx ...(1)
where RFa and RFx are the response factors for reference compound a and reference compound x, respectively.
RFa=Aa/ma …(2)
ここで、Aaとmaはそれぞれ、マスクロマトグラムにおける参照化合物aのピーク面積と重量(mg)である。また、参照化合物aの重量maは次式(3)で表される。
ma=M×Ca …(3)
ここで、MとCaはそれぞれ、標準試料の重量(kg)と、標準試料に含まれる参照化合物aの濃度(mg/kg)である。 The response factor RF a of reference compound a is represented by the following formula (2). Note that the following formulas apply not only to the reference compound a but also to the standard compound x.
RF a =A a /m a …(2)
where A a and ma are the peak area and weight (mg) of reference compound a in the mass chromatogram, respectively. Also, the weight ma of the reference compound a is represented by the following formula (3).
m a = M × C a … (3)
Here, M and C a are the weight (kg) of the standard sample and the concentration (mg/kg) of the reference compound a contained in the standard sample, respectively.
次に、分析対象試料をスクリーニングする手順を説明する。本実施例のPy-GC-MS1では、相対応答係数データベースを用いる規制化合物のスクリーニング、及び各規制化合物の検量線を用いる規制化合物のスクリーニングの2通りのスクリーニングを行うことができる。 2. Screening Procedure for Regulated Compounds Next, a procedure for screening a sample to be analyzed will be described. The Py-GC-MS1 of this embodiment can perform two types of screening, ie, screening of controlled compounds using a relative response coefficient database and screening of controlled compounds using a calibration curve for each controlled compound.
図6に示すフローチャートを参照して、相対応答係数データベースを用いて規制化合物をスクリーニングする手順を説明する。 2-1. Screening of Regulated Compounds Using the Relative Response Factor Database A procedure for screening regulated compounds using the relative response factor database will now be described with reference to the flow chart shown in FIG.
Ix=100(Cn+i-Cn){(tx-tn)/(tn+i-tn)}+100Cn …(4)
ここで、Cn, Cn+iはそれぞれ当該化合物の保持時間を挟んで保持時間が前後に位置するn-アルカンの炭素数、txは化合物xの保持時間、tn, tn+iは当該化合物の保持時間を挟んで保持時間が前後に位置するn-アルカンの保持時間である。なお、各規制化合物の保持指標が予め得られている場合には、ここでのn-アルカン試料の測定を省略し、分析対象試料の測定時にのみn-アルカン試料の測定を行い、n-アルカン試料に含まれる各化合物の保持時間と予め得られている規制化合物の保持指標の値から各規制化合物の保持時間を推定するようにしてもよい。 In addition to measuring standard samples, n-alkane samples are also measured. An n-alkane sample is a standard sample containing multiple compounds with different hydrocarbon chain lengths, and is used to obtain a retention index based on the retention time of each compound. As described in
Ix= 100(Cn +i -Cn){( tx -tn)/( tn +i - tn ) } + 100Cn ...(4)
Here, C n , C n+i are the numbers of carbon atoms in n-alkanes positioned before and after the retention time of the compound, t x is the retention time of compound x, t n , t n+i are the retention times of the n-alkanes before and after the retention time of the compound. If the retention index of each regulated compound is obtained in advance, the measurement of the n-alkane sample is omitted here, and the n-alkane sample is measured only when the sample to be analyzed is measured. The retention time of each regulated compound may be estimated from the retention time of each compound contained in the sample and the previously obtained retention index value of the regulated compound.
図7に示すフローチャートを参照して、各規制化合物の検量線を用いて規制化合物をスクリーニングする手順を説明する。なお、相対応答係数データベースを用いる規制化合物のスクリーニングと同じ手順については適宜、説明を省略する。 2-2. Screening of Regulated Compounds Using Calibration Curves of Each Regulated Compound A procedure for screening a regulated compound using a calibration curve of each regulated compound will be described with reference to the flowchart shown in FIG. The description of the same procedure as the screening of controlled compounds using the relative response factor database will be omitted as appropriate.
上述した複数の例示的な実施例は、以下の態様の具体例であることが当業者により理解される。 [Aspect]
It will be appreciated by those skilled in the art that the multiple exemplary embodiments described above are specific examples of the following aspects.
本発明の一態様に係るフタル酸エステル類及び臭素系難燃化合物の測定方法は、
フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を含有する試料を加熱して該試料に含まれる対象化合物を気化させ、
内部に前記対象化合物を分離するための固定相が設けられた分離カラムと、接続部品を用いることなく該分離カラムの入口側に該分離カラムと一体に設けられたガードカラムとを有する分析カラムを、前記対象化合物を気化させる際の最高温度よりも低い温度に温調し、
気化させた前記対象化合物を前記分析カラムに導入し、
前記分離カラムから流出する対象化合物を検出する
ものである。 (Section 1)
A method for measuring a phthalate ester and a brominated flame retardant compound according to one aspect of the present invention comprises:
heating a sample containing a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group to vaporize the target compound contained in the sample;
An analysis column having a separation column internally provided with a stationary phase for separating the target compound, and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts. , adjusting the temperature to a temperature lower than the maximum temperature at which the target compound is vaporized,
introducing the vaporized target compound into the analysis column;
A target compound flowing out from the separation column is detected.
本発明の別の一態様は、フタル酸エステル類及び臭素系難燃化合物の測定方法を実施する際に用いるガスクロマトグラフカラムであって、
フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を分離するための固定相が設けられた分離カラムと、
接続部品を用いることなく前記分離カラムの入口側に該分離カラムと一体に設けられたガードカラムと
を備える。 (Section 8)
Another aspect of the present invention is a gas chromatograph column used in carrying out a method for measuring phthalates and brominated flame retardant compounds,
a separation column provided with a stationary phase for separating a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group;
and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts.
第1項に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、
前記対象化合物をパイロライザーにおいて気化させる。 (Section 2)
In the method for measuring phthalates and brominated flame retardants according to
The target compound is vaporized in the pyrolyzer.
第1項又は第2項に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、
前記分析カラムのうち、前記分離カラムにのみ固定相が設けられている。 (Section 3)
In the method for measuring the phthalates and brominated flame retardant compounds according to
Of the analysis columns, only the separation column is provided with a stationary phase.
第1項から第3項のいずれかに記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、
前記ガードカラムの長さが50cm以上4m以下である。 (Section 4)
In the method for measuring phthalates and brominated flame retardant compounds according to any one of
The guard column has a length of 50 cm or more and 4 m or less.
第1項から第4項のいずれかに記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、
前記分離カラムの長さが10m以上30m以下である。 (Section 5)
In the method for measuring phthalates and brominated flame retardant compounds according to any one of
The separation column has a length of 10 m or more and 30 m or less.
第1項から第5項のいずれかに記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、
前記分離カラムから流出する対象化合物を質量分離して検出する。 (Section 6)
In the method for measuring phthalates and brominated flame retardant compounds according to any one of
The target compound flowing out from the separation column is detected by mass separation.
第1項から第6項のいずれかに記載のフタル酸エステル類及び臭素系難燃化合物の測定方法において、さらに、
前記対象化合物の含有量が予め決められた範囲内であるか否かに基づいて、前記試料をスクリーニングする。 (Section 7)
In the method for measuring phthalates and brominated flame retardant compounds according to any one of
The sample is screened based on whether the content of the target compound is within a predetermined range.
10…ガスクロマトグラフ部
11…試料気化室
12…パイロライザー
13…キャリアガス流路
14…カラム(分析カラム)
141…ガードカラム
142…分離カラム
1421…固定相
15…カラムオーブン
20…質量分析部
21…真空チャンバ
22…電子イオン化源
23…イオンレンズ
24…四重極マスフィルタ
25…イオン検出器
30…制御・処理部
31…記憶部
311…相対応答係数データベース
32…基準化合物決定部
33…標準試料測定部
34…分析対象試料測定部
35…基準化合物定量部
36…参照化合物定量部
37…スクリーニング部
4…入力部
5…表示部 DESCRIPTION OF
141...
Claims (8)
- フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を含有する試料を加熱して該試料に含まれる対象化合物を気化させ、
内部に前記対象化合物を分離するための固定相が設けられた分離カラムと、接続部品を用いることなく該分離カラムの入口側に該分離カラムと一体に設けられたガードカラムとを有する分析カラムを、前記対象化合物を気化させる際の最高温度よりも低い温度に温調し、
気化させた前記対象化合物を前記分析カラムに導入し、
前記分離カラムから流出する対象化合物を検出する
ものである、フタル酸エステル類及び臭素系難燃化合物の測定方法。 heating a sample containing a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group to vaporize the target compound contained in the sample;
An analysis column having a separation column internally provided with a stationary phase for separating the target compound, and a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts. , adjusting the temperature to a temperature lower than the maximum temperature at which the target compound is vaporized,
introducing the vaporized target compound into the analysis column;
A method for measuring phthalate esters and brominated flame-retardant compounds, wherein the target compound flowing out from the separation column is detected. - 前記対象化合物をパイロライザーにおいて気化させる、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 The method for measuring phthalate esters and brominated flame retardant compounds according to claim 1, wherein the target compound is vaporized in a pyrolyzer.
- 前記分析カラムのうち、前記分離カラムにのみ固定相が設けられている、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 The method for measuring phthalates and brominated flame-retardant compounds according to claim 1, wherein only the separation column of the analysis columns is provided with a stationary phase.
- 前記ガードカラムの長さが50cm以上4m以下である、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 The method for measuring phthalates and brominated flame retardant compounds according to claim 1, wherein the guard column has a length of 50 cm or more and 4 m or less.
- 前記分離カラムの長さが10m以上30m以下である、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 The method for measuring phthalates and brominated flame-retardant compounds according to claim 1, wherein the separation column has a length of 10 m or more and 30 m or less.
- 前記分離カラムから流出する対象化合物を質量分離して検出する、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 The method for measuring phthalates and brominated flame-retardant compounds according to claim 1, wherein the target compounds flowing out from the separation column are detected by mass separation.
- さらに、前記対象化合物の含有量が予め決められた範囲内であるか否かに基づいて、前記試料をスクリーニングする、請求項1に記載のフタル酸エステル類及び臭素系難燃化合物の測定方法。 Further, the method for measuring phthalate esters and brominated flame retardant compounds according to claim 1, wherein the sample is screened based on whether the content of the target compound is within a predetermined range.
- フタル酸エステル類、ポリ臭化ビフェニル群、及びポリ臭化ジフェニルエーテル群の少なくとも1つに属する対象化合物を分離するための固定相が設けられた分離カラムと、
接続部品を用いることなく前記分離カラムの入口側に該分離カラムと一体に設けられたガードカラムと
を備えるガスクロマトグラフカラム。 a separation column provided with a stationary phase for separating a target compound belonging to at least one of the phthalates, the polybrominated biphenyl group, and the polybrominated diphenyl ether group;
A gas chromatograph column comprising: a guard column provided integrally with the separation column on the inlet side of the separation column without using connecting parts.
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PCT/JP2021/023636 WO2022269763A1 (en) | 2021-06-22 | 2021-06-22 | Method for measuring phthalic-acid-ester- and bromine-based flame-retardant compound, and gas chromatography for use in said method |
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Non-Patent Citations (4)
Title |
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"Development of UA Guard", 1 April 2020 (2020-04-01), Retrieved from the Internet <URL:https://www.frontier-lab.com/assets/file/technical-note/UAT-008.pdf> * |
"InertCap series. Build-in Guard Column: InertCap ProGuard", 29 March 2019 (2019-03-29), Retrieved from the Internet <URL:https://ebook-gls.meclib.jp/generalcatalog/book/#target/page_no=377> * |
BJORKLUND, JONAS ET AL.: "Influence of the injection technique and column system on gas chromatographic determination of polybrominated diphenyl ethers", JOURNAL OF CHROMATOGRAPHY A., vol. 1041, 2004, pages 201 - 210, XP004519493, DOI: 10.1016/j.chroma.2004.04.025 * |
KUDO, YUKIHIKO ET AL.: "Development of a screening method for phthalate ester in polymers using a quantitative database in combination with pyrolyzer/thermal desorption gas chromatography mass spectrometry", JOURNAL OF CHROMATOGRAPHY A, vol. 1602, 2019, pages 441 - 449, XP085757595, DOI: 10.1016/j.chroma.2019.06.014 * |
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