JP2023077724A - Analysis method of high polymer material - Google Patents

Abstract

To provide an analysis method of a high polymer material, the method enabling information on a component contained in a high polymer material to be surely acquired by a double shot method.SOLUTION: An analysis method of a high polymer material is performed in the below-mentioned steps comprising: a selection step in which on the basis of a result of a generated gas analysis method of a sample, a temperature region where a first analysis target component is generated, is selected; a first capturing step in which selective introduction means and suction means 5 are activated, the sample is heated and the included component is thermally desorbed, a first gas phase component mixture generated in the temperature region where the first analysis target component is generated, is introduced into a first column 31 and the first analysis target component is captured to the first column 31; a gasification step in which the suction means 5 is stopped and the first analysis target component is gasified, then the first analysis target component is introduced into a second column 32 and is separated, and is detected by detection means 41; a second capturing step in which division introduction means 35 is opened, the selective introduction means is stopped, the suction means 5 is actuated, the sample is thermally decomposed, the second analysis target component is captured to the first column 31, the suction means 5 is stopped for gasifying the second analysis target component and the gasified second analysis target component is introduced into the second column 32 and is separated; and a detection step in which the second analysis target component is detected by the detection means 41.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for analyzing polymeric materials.

Gas chromatography is conventionally known as a method for analyzing gas phase components. As a gas phase component analyzer (gas chromatograph) used for gas chromatography, for example, a heating means for heating a sample to generate a gas phase component mixture, and the gas generated by the heating means connected to the heating means. A separation column that separates a phase component mixture into individual components, a constant temperature bath (oven) that houses the separation column, and a detector that is connected to the separation column and detects the individual components separated by the separation column. are known.

The heating means thermally decomposes or volatilizes the sample, or heats the sample to thermally desorb components contained in the sample to generate the gas phase component mixture. A mass spectrometry detector (MS) or the like is used for the detector.

When analyzing the composition of a polymeric material using the gas phase component analyzer, for example, first, the polymeric material is heated to a temperature of about 300° C., and is contained in the polymeric material in a free state. thermally desorbing the components to form a first gas phase component mixture; introducing the first gas phase component mixture into the separation column to separate the individual gas phase components; is detected with a detector such as the mass spectrometry detector (MS). Next, the polymeric material after the components contained in the free state are thermally desorbed is instantaneously thermally decomposed at a temperature of about 600° C. to generate a second gas phase component mixture, and the second The gas phase component mixture is introduced into the separation column to separate into individual gas phase components, and the separated individual gas phase components are detected by a detector such as the mass spectrometer (MS).

Said method is sometimes called a double-shot method, since said thermal desorption is followed by said pyrolysis.

By the way, ordinary polymer materials contain additives such as antioxidants and ultraviolet absorbers in an amount of 0.1% by mass or less based on the total amount in order to improve performance. For example, ethylene-vinyl acetate copolymer resin contains, as the additive, a phosphorus-based processing stabilizer called Irgafos 168 (tris(2,4-di-tert-butylphenyl)phosphite).

For quality control purposes, it is necessary to analyze the composition of the polymeric material containing the additives. When the analysis of the composition of the polymer material is performed by the double-shot method, the analysis of the first gas phase component mixture generated by thermal desorption of the polymer material reveals the components contained in the free state such as the additives. It is believed that information can be obtained and that analysis of the second gas phase component mixture produced by thermal decomposition of the polymeric material can provide information about the polymeric material itself.

Further, in the gas phase component analyzer, a part of the gas phase component mixture, for example 1 to 10%, is introduced into the separation column through an injection port connecting the heating means and the separation column, while the remainder is introduced into the separation column. There is known a device provided with split introduction means (split vent) for discharging a certain 90 to 99% of the gas to the outside (see, for example, Patent Document 1). At this time, the ratio of the component to be introduced into the separation column to the total amount of the gas phase component mixture is called a split ratio, and the split ratio is usually a predetermined fixed value in the gas phase component analyzer.

JP 2018-66618 A

When the composition of the polymer material is analyzed by the double-shot method, the split ratio is preferably small for the analysis of the second gas phase component mixture generated by thermal decomposition of the polymer material itself. . However, when the split ratio is decreased, the amount of the gas phase component mixture introduced into the separation column is reduced. When the content of the component contained in the free state relative to the entire polymer material is as small as 0.1% by mass or less, sufficient detection intensity cannot be obtained. , there is a problem that the analysis of the first gas phase component mixture produced by thermal desorption of the polymer material cannot be performed.

Therefore, the first gas phase component mixture generated by thermal desorption of the polymer material is derived from the components contained in the polymer material in a free state, and the entire polymer material of the components contained in the free state is as small as 0.1% by mass or less, the split ratio is preferably large for analysis of the first gas phase component mixture produced by the thermal desorption. However, when the split ratio is increased, the second gas phase component mixture generated by thermal decomposition of the polymer material contains a large amount of non-analyte components such as solvent, unreacted methylating agent, and silylating agent. In some cases, the separation column deteriorates due to the non-analyte component, or the detector malfunctions, making it impossible to analyze the second gas phase component mixture produced by thermal decomposition of the polymer material. be.

In order to solve the above problem, when analyzing a first gas phase component mixture generated by thermal desorption of the polymer material, and analyzing a second gas phase component mixture generated by thermal decomposition of the polymer material itself It is conceivable to change the split ratio of the gas phase component analyzer depending on when the analysis is performed.

However, in the gas-phase component analyzer, the split ratio is usually a predetermined fixed value, which is difficult to change.

The present invention solves this problem by changing the split ratio of the gas phase component analyzer when analyzing the composition of a polymer material by the double shot method using the gas phase component analyzer. To provide a method for analyzing a polymer material that can reliably obtain information on both components such as additives contained in the polymer material in a free state and the components of the polymer material itself. aim.

The present applicant has already filed a patent application for a gas-phase component analyzer capable of preventing deterioration of the separation column and detector due to non-analyte components and achieving excellent detection sensitivity (patent application 2020-215423). The gas phase component analyzer described in the patent application includes heating means for heating a sample to generate a gas phase component mixture, a first column into which the gas phase component mixture generated by the heating means is introduced, and the an injection port that connects the heating means and the first column; a second column that is a separation column that is connected to the first column via the connecting means; and the first column and the second column. and said connection means, and a detection means for detecting individual gas phase components separated by said second column, wherein suction means connected to said connection means and a split vent provided at the injection port and serving as divided introduction means for introducing part of the gas phase component mixture produced by the heating means into the first separation column while discharging the remainder to the outside. I have.

According to the gas phase component analyzer described in the patent application, first, the suction means is operated, the sample is put into or injected into the heating means, and the sample is heated to generate the gas phase component mixture. Let At this time, the suction means is further operated for a predetermined period of time after the sample is introduced or injected. By operating the suction means, the split vent does not substantially operate, the generated gas phase component mixture is sucked, and the entire amount of the gas phase component mixture flows into the first column through the injection port. introduced into

The gas phase component mixture contains a high boiling point, low volatility analyte component and a low boiling point, high volatility non-analyte component such as a solvent, wherein the first column has a boiling point of the non-analyte component Since the temperature is set to be higher than the boiling point of the analyte component, the non-analyte component is further sucked toward the suction means without being captured by the first column, but the analyte component is selectively is trapped in the first column at .

Here, said first column is connected to said second column via said connection means, and said suction means is also connected to said connection means. However, since the second column acts as a flow path resistance, the non-analyte components are not introduced into the second column, but are sucked into the suction means and released to the outside through the suction means. be done.

After the non-analyte component is released to the outside, the suction means is stopped after the predetermined time, and the temperature of the constant temperature bath is raised to a temperature at which the analyte component can be vaporized. In this way, the analyte trapped in the first column is vaporized. Further, when the suction means is stopped, the carrier gas whose flow rate is controlled by the dividing introduction means causes the component to be analyzed to move toward the connecting means.

At this time, the suction means is stopped, and the direction of connection of the connection means to the suction means is closed. introduced into Since the second column is a separation column, the analyte components introduced into the second column are separated into individual gas phase components, and the individual gas phase components that have passed through the second column are separated into the individual gas phase components. It can be detected by a detection means.

The present inventors improved the gas phase component analysis device described in the patent application when analyzing the polymer material as the sample by the double shot method, and further improved the gas phase component analysis method described in the patent application. By combining with the generated gas analysis method, the components of the polymer material itself and the components contained in the polymer material such as additives in a free state can be analyzed without changing the split ratio of the gas phase component analyzer. The present invention has been arrived at by conceiving that both information can be reliably obtained.

Therefore, in order to achieve the above object, the method for analyzing a polymeric material of the present invention comprises heating means for heating a sample to generate a gas phase component mixture, and introduction of the gas phase component mixture generated by the heating means. an inlet connecting the heating means and the first column; a second column which is a separation column connected to the first column via a connecting means; A constant temperature bath containing one column, the second column, and the connection means, detection means for detecting individual gas phase components separated by the second column, and suction connected to the connection means. dividing introduction means provided in the injection port for introducing a part of the gas phase component mixture produced by the heating means into the first separation column and discharging the remainder to the outside; and the heating means. Part of the gas phase component mixture produced in 1. is selectively introduced into the first separation column, while the remaining part is discharged to the outside. An analytical method, comprising the step of selecting a temperature range in which the first analyte component is generated from the results of the generated gas analysis method of the sample; heating the sample in a heating means to thermally desorb components contained in the sample in a free state from the sample to form a first gas phase component mixture and generating the first analyte; selectively introducing the first gas phase component mixture generated in a temperature region to the first column through the injection port, and performing the first analysis contained in the first gas phase component mixture capturing the target component in the first column; after capturing the first analyte component in the first column, stopping the selective introduction means and the suction means; to a temperature at which the first analyte is vaporizable to vaporize the first analyte; and introducing the vaporized first analyte into the second column, a step of separating into individual gas phase components and detecting the separated individual gas phase components with the detection means; opening the divided introduction means, stopping the selective introduction means, and operating the suction means; heating the sample after the components contained in the free state are thermally desorbed in the heating means to thermally decompose the sample to produce a second gas phase component mixture; A portion of the second gas phase component mixture produced is introduced into the first column by the divided introduction means, while the remainder of the second gas phase component mixture is discharged to the outside and introduced into the first column. trapping on the first column a second analyte contained in the introduced second gas phase mixture; after trapping the second analyte on the first column; , stopping the suction means and heating the first column to a temperature at which the second analyte component can be vaporized to vaporize the second analyte; introducing the target component into the second column, separating it into individual gas phase components, and detecting the separated individual gas phase components with the detection means.

In the method for analyzing a polymer material of the present invention, first, the polymer material as the sample is analyzed by the evolved gas analysis method, and the temperature range in which the first component to be analyzed is generated is selected from the results.

In the method for analyzing a polymeric material of the present invention, next, the gas phase component analyzer is used to first heat the sample to thermally desorb the components contained in the sample in a free state to form the first A gas phase component mixture is generated, the first gas phase component mixture is introduced into the separation column and separated into individual gas phase components, and the separated individual gas phase components are detected by a detector. Next, using the gas phase component analyzer, the sample after the components contained in the free state are thermally desorbed is instantaneously thermally decomposed to generate a second gas phase component mixture, and the second gas phase component mixture is is introduced into the separation column and separated into individual gas phase components, and the separated individual gas phase components are detected by a detector.

Here, the gas phase component analysis device used in the method for analyzing a polymer material of the present invention is a gas phase component analysis device provided with a split vent as a split introduction means according to Japanese Patent Application No. 2020-215423, and further, the heating means A part of the gas phase component mixture produced in (1) is selectively introduced into the first separation column, while the remainder is discharged to the outside.

Therefore, in the method for analyzing a polymeric material of the present invention, in the gas phase component analyzer, the sample is first heated in the heating means while the selective introduction means and the suction means are in operation. , thermally desorbs from the sample the components contained in the sample in a free state. In this way, the first gas-phase component mixture is produced which consists of the components contained in the sample in a free state.

At this time, in the method for analyzing a polymeric material of the present invention, the first gas phase component mixture generated in the temperature range where the first component to be analyzed is generated by the selective introduction means is passed through the injection port. While selectively introducing into the first column, the first gas phase component mixture produced outside the temperature range is discharged to the outside. As a result, the first analyte contained in the first gas phase component mixture generated in the temperature range is trapped in the first column.

Next, when the first analyte component is trapped in the first column, the selective introduction means and the suction means are stopped, and the first column is moved to the position where the first analyte component is trapped. The first analyte is vaporized by heating to a vaporizable temperature, and the vaporized first analyte is introduced into the second column. Since the second column is a separation column, the first analyte introduced into the second column is separated into individual gas phase components in the second column, and the separated individual A gas phase component is detected by the detecting means.

Individual gas phase components constituting the first component to be analyzed are, for example, components derived from additives contained in the polymer material in an amount of 0.1% by mass or less of the total, and are very It is rare. However, according to the method for analyzing a polymeric material of the present invention, as described above, the first analyte component is selected from the first gas phase component mixture generated by thermal desorption. Only the first gas phase component mixture produced in the temperature region is selectively introduced into the first column and captured. As a result, the concentration of the first analyte component in the first gas phase component mixture captured by the first column increases, and when detected by the detecting means, sufficient detection intensity is obtained. can be obtained, and information on the first analyte component can be reliably obtained.

In the method for analyzing a polymeric material of the present invention, next, the divided introduction means is opened, the selective introduction means is stopped, and the suction means is operated, and the polymer is contained in the heating means in a free state. The sample is thermally decomposed by heating the sample after the components to be desorbed are thermally desorbed. In this way, the second gas phase component mixture is produced by thermal decomposition of the polymer material itself that constitutes the sample.

At this time, in the method for analyzing a polymeric material of the present invention, since the dividing introduction means is opened, the generated second gas phase component mixture is partially introduced into the first gas phase component mixture by the dividing introduction means. column, while the remainder is discharged to the outside. Then, the second gas phase component mixture introduced into the first column is maintained while the second analyte component contained in the second gas phase component mixture is trapped in the first column. , non-analyte components are sucked by the suction means and discharged to the outside.

Next, when the second analyte component is trapped in the first column, the suction means is stopped and the first column is heated to a temperature at which the second analyte component can be vaporized. to vaporize the second analyte, and introduce the vaporized second analyte into the second column. Since the second column is a separation column, the second analyte introduced into the second column is separated into individual gas phase components in the second column, and the separated individual A gas phase component is detected by the detecting means.

The second gas phase component mixture generated by thermal decomposition of the polymer material itself may contain a large amount of non-analyte components such as solvents. However, according to the method for analyzing a polymeric material of the present invention, as described above, the second gas phase component mixture generated by the thermal decomposition of the polymeric material itself is partly is introduced into the first column, and the second gas phase component mixture introduced into the first column is such that only the second analyte contained therein is trapped in the first column. On the other hand, non-analytical components are sucked by the suction means and discharged to the outside. As a result, only the second analysis target component is introduced into the second column and separated into individual gas phase components, and can be reliably detected by the detection means, thereby performing the second analysis. Information on target components can be obtained.

Therefore, according to the method for analyzing a polymer material of the present invention, a gas phase component analyzer obtained by adding the selective introduction means to the gas phase component analyzer described in Japanese Patent Application No. 2020-215423 is used to analyze the polymer by the double shot method. Components such as additives contained in the polymer material in a free state without changing the split ratio of the gas phase component analyzer by combining the generated gas analysis method when analyzing the material and the components of the polymer material itself can be reliably obtained.

In the method for analyzing a polymer material of the present invention, the generated gas analysis method can be performed using a known device. In the gas-phase component analysis apparatus added, instead of the first column and the second column, a metal tube having an inactivated inner surface can be used.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory cross-sectional view showing one structural example of a gas-phase component analyzer used in the method for analyzing a polymer material of the present invention; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory cross-sectional view showing one structural example of a gas-phase component analyzer used for the generated gas analysis method in the polymer material analysis method of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows one analysis example of the generated gas analysis method of the polymeric material by the analysis method of the polymeric material of this invention, the lower stage is a thermogram obtained by the generated gas analysis method, and the upper stage is the zone A of this thermogram. Mass spectra of included components. FIG. 3 is a diagram showing an example of analysis of a polymer material by the method for analyzing a polymer material of the present invention. The bottom row is an extracted ion chromatogram of the component at m/z 647 among the components contained in zone A in FIG. FIG. 5 is a diagram showing an analysis example of a polymer material by the method for analyzing a polymer material of the present invention, and is a pyrogram of a gas phase component mixture generated by thermal decomposition after thermal desorption in FIG. 4 .

Embodiments of the present invention will now be described in more detail with reference to the accompanying drawings.

The method for analyzing a polymeric material according to the present embodiment can be carried out using the gas phase component analyzer 1 shown in FIG. 1 and the gas phase component analyzer 11 shown in FIG.

The gas-phase component analyzer 1 shown in FIG. 1 is a gas chromatograph used for gas chromatography-mass spectrometry (GC/MS). and a detection device 4 connected to the .

The heating device 2 includes a heating furnace 21 made of a chemically inert hollow cylindrical quartz tube, a heater 22 provided around the heating furnace 21, and a GC inlet 23 into which the tip of the heating furnace 21 is inserted. and The heater 22 heats the heating furnace 21 under predetermined conditions by means of a temperature control device (not shown). The heating furnace 21 is connected to the upper part of the GC inlet 23 by a heated pipe or the like, or is detachably attached to the upper part of the GC inlet 23 without using the pipe or the like. Further, the heating furnace 21 may be made of a stainless steel tube made inert by forming a quartz thin film on the inner surface thereof instead of the quartz tube.

The GC injection port 23 is provided with a heater (not shown) which, like the heater 22, heats the GC injection port 23 under predetermined conditions by a temperature control device (not shown). When the heating furnace 21 is not connected or attached to the upper portion of the GC injection port 23, a septum (not shown) is attached to the upper end.

The heating device 2 includes a sample introduction section 24 connected above the heating furnace 21 , and a carrier gas conduit 25 as carrier gas introduction means for introducing a carrier gas into the heating furnace 21 is connected to the sample introduction section 24 . there is The other end of carrier gas conduit 25 is connected to carrier gas source 27 via carrier gas flow controller 26 . Also, the carrier gas conduit 25 is connected to the GC injection port 23 when the heating furnace 21 is not connected or mounted above the GC injection port 23 .

As a result, the carrier gas supplied from the carrier gas source 27 is adjusted to a predetermined flow rate by the carrier gas flow controller 26 and introduced into the heating furnace 21 or the GC inlet 23 .

The constant temperature bath 3 includes a pre-column 31 as a first column, a main separation column 32 as a second column which is a separation column, and a three-way pipe as connecting means for connecting the pre-column 31 and the main separation column 32. (T-tube) 33 is accommodated. One end of the pre-column 31 is inserted into the GC injection port 23 and faces the tip of the heating furnace 21 , while the other end is connected to the main separation column 32 via a three-way tube 33 . The main separation column 32 has one end connected to the pre-column 31 via a three-way tube 33 and the other end connected to a detection means 41 such as a quadrupole mass spectrometry detector housed in the detection device 4 . ing.

The three-way pipe 33 connects the pre-column 31 and the main separation column 32 in a straight line, and is connected to the exhaust conduit 34 in a direction orthogonal to the connection direction between the pre-column 31 and the main separation column 32. is connected to a suction pump 5 such as a vacuum pump provided outside the constant temperature bath 3 .

The pre-column 31 has, for example, an inner diameter of 0.25 mm, a length of 1 m, and a fixed layer of 0.25 μm in thickness made of a copolymer of diphenylpolysiloxane and dimethylpolysiloxane at a molar ratio of 5:95 on the inner surface. or a capillary column with an inner diameter of about 0.1 to 0.5 mm and a length of 0.5 to 19 m, the inner surface of which is coated with various polymers, or the inner surface of which is chemically inactivated without coating the polymer. A capillary tube can be used. The main separation column 32 has, for example, an inner diameter of 0.25 mm, a length of 30 m, and a thickness of 0.25 μm made of a copolymer of diphenylpolysiloxane and dimethylpolysiloxane at a molar ratio of 5:95 on the inner surface. A stainless steel capillary column can be used with a fixed bed of .

The pre-column 31 is detachable from the GC injection port 23 and the three-way tube 33, and the pre-column 31 can be selected according to the object to be analyzed.

As the detection means 41, in addition to a mass spectrometry detector (MS) such as the quadrupole mass spectrometry detector, a flame ionization detector (FID), an electron capture detector (ECD), or the like can be used.

In addition, the gas phase component analyzer 1 is provided with a split vent 35 as split introduction means for introducing part of the gas phase component mixture into the pre-column 31 and discharging the remainder to the GC inlet 23 . . The split vent 35 is openable and closable by an on-off valve (not shown). while the remainder is discharged to the outside. In the split vent 35, the split ratio, which is the ratio of the component introduced into the pre-column 31 to the total amount of the gas phase component mixture, is set to a predetermined value, for example, 1/100.

In addition, the gas phase component analyzer 1 selectively introduces a part of the gas phase component mixture into the pre-column 31 via the GC inlet 23, while discharging the remaining portion to the outside. A conduit 36 is provided. The purge gas conduit 36 is connected via an on-off valve 37 to a purge gas flow controller 38 which is connected to a purge gas source 39 .

When the gas phase component mixture produced by the heating means 21 is discharged to the outside, the selective introduction means opens the on-off valve 37 and adjusts the purge gas supplied from the purge gas source 39 to a predetermined flow rate by the purge gas flow control device 38. It is conditioned and supplied to the GC inlet 23 through the purge gas conduit 36 . Then, the purge gas supplied to the GC injection port 23 discharges the gas phase component mixture to the outside through the split vent 35 . On the other hand, the selective introduction means closes the on-off valve 37 and stops the supply of the purge gas to the GC injection port 23 when introducing the gas phase component mixture generated by the heating means 21 into the pre-column 31 . As a result, the selective introduction means can selectively introduce a portion of the gas phase component mixture into the pre-column 31 while discharging the remainder to the outside.

In this embodiment, the selective introduction means is such that the purge gas supplied to the GC injection port 23 discharges the gas phase component mixture to the outside through the split vent 35. A discharge conduit may be provided for discharging the purge gas and the gas phase component mixture to the outside.

Further, the gas phase component analyzer 11 shown in FIG. 2 is a gas phase component analyzer used for generated gas analysis-mass spectrometry (EGR / MS), and the pre-column 31 and main separation of the gas phase component analyzer 1 shown in FIG. Except for providing an EGA column 40 instead of the column 32, it has the same configuration as the gas-phase component analyzer 1. The EGA column 40 has an inner surface of 0.15 mm in inner diameter and 2.5 m in length, for example. can be used.

Next, a method for analyzing a polymer material according to the present embodiment using the gas phase component analyzer 1 shown in FIG. 1 and the gas phase component analyzer 11 shown in FIG. 2 will be described.

The analysis method of the polymer material of the present embodiment is, for example, the composition of the polymer material containing additives such as antioxidants and ultraviolet absorbers in an amount of 0.1% by mass or less of the total amount. It is used when analyzing by a combination of the analytical method and the double-shot method.

Therefore, the method for analyzing a polymeric material according to the present embodiment will now be described with an example of analyzing the composition of an ethylene-vinyl acetate copolymer (EVA) as a polymeric material. The EVA contains a phosphorus-based processing stabilizer called Irgafos 168 (tris(2,4-di-tert-butylphenyl)phosphite) as an additive.

In the method for analyzing a polymeric material according to the present embodiment, first, in the gas phase component analyzer 11 shown in FIG. 2, the split vent 35 was opened to set the split ratio to 1/50, and the selective introducing means was stopped. In this state, a carrier gas such as helium or nitrogen is supplied to the heating furnace 21 from the carrier gas source 27 through the flow control device 26 at a flow rate of, for example, 1 ml/min. For example, it is heated to 100°C. Next, 0.1 to 0.2 mg of EVA contained in the sample cup 6 is put into the heating furnace 21 as a sample. Then, for example, the temperature of the heating furnace 21 is raised from 100° C. to 700° C. at a rate of 20° C./min, and the change in the amount of gas generated from the polymer material is observed. The thermogram shown can be obtained.

In the method for analyzing a polymeric material according to the present embodiment, next, by comparing the mass spectrum of the thermogram profile shown in the lower part of FIG. set. For example, the mass spectrum of zone A, which is the profile of the thermogram shown in the lower part of FIG. 3, is shown in the upper part of FIG.

From the mass spectrum in the upper part of FIG. 3, it can be determined that zone A contains oxidized Irgaphos 168 with m/z 647, which is the additive to be analyzed first. Therefore, the temperature range of 300 to 360° C. corresponding to zone A is selected as the temperature range in which the first component to be analyzed is generated.

In the method for analyzing a polymer material of this embodiment, next, in the gas phase component analyzer 1 shown in FIG. The heating furnace 21 is heated to a predetermined temperature, for example, 100° C. by the heater 22 while the carrier gas is supplied to the heating furnace 21 at a flow rate of, for example, 2 ml/min. Next, with the split vent 35 opened and the selective introduction means and the suction pump 5 in operation, 0.2 mg of EVA contained in the sample cup 6 is put into the heating furnace 21 as a sample. In addition, the selective introducing means can open and close the on-off valve 37 as required in the activated state.

Then, for example, the temperature of the heating furnace 21 is raised from 100° C. to 380° C. at a rate of 20° C./min, and held at 380° C. for 1 minute. A component containing Irgaphos 168 or the like as the additive is thermally desorbed from the polymeric material to form a first gas phase component mixture.

At this time, in the present embodiment, the on-off valve 37 is opened and the purge gas supplied from the purge gas source 39 is controlled by the purge gas flow controller 38 outside the temperature range of 300 to 360° C. corresponding to zone A in the lower thermogram of FIG. The gas is adjusted to a predetermined flow rate by the purge gas conduit 36 and supplied to the GC injection port 23 . Then, the purge gas supplied to the GC injection port 23 discharges the first gas phase component mixture produced outside the temperature range of 300 to 360° C. corresponding to the zone A to the outside through the split vent 35. do.

On the other hand, in the temperature range of 300 to 360° C. corresponding to zone A, the on-off valve 37 is closed, the supply of the purge gas to the GC inlet 23 is stopped, and the split vent 35 is closed. As a result, the first gas phase component mixture produced in the temperature range of 300 to 360° C. corresponding to zone A is sucked by the suction pump 5 and selectively introduced into the pre-column 31 .

After the first gas phase component mixture is produced, the polymer material is stored in the sample cup 6 and evacuated to a region that is not affected by the heating of the heating furnace 21 .

At this time, the temperature of the pre-column 31 is set to, for example, 40°C. is trapped. On the other hand, among the components contained in the first gas phase component mixture, components with a boiling point of 40° C. or less are sucked by the suction pump 5 and discharged to the outside as non-analytical components.

Next, when the first component to be analyzed generated in the temperature range of 300 to 360° C. corresponding to zone A is trapped in the precolumn 31, the suction pump 5 is stopped and the carrier gas is supplied to, for example, 200 ml. /min, the pre-column 31 is heated to a temperature at which the first analysis target component can be vaporized, thereby vaporizing the first analysis target component. The operation of heating the pre-column 31 to a temperature at which the first component to be analyzed can be vaporized is specifically performed by raising the temperature of the constant temperature bath 3 . For example, the temperature of the constant temperature bath 3 is maintained at 40 ° C. for 2 minutes, the temperature is raised from 40 ° C. to 320 ° C. at a rate of 20 ° C./min, and held at 320 ° C. for 14 minutes, so that the first analyte component is vaporized and the vaporized first analyte is introduced into main separation column 32 via three-way tube 33 . Since the main separation column 32 is a separation column, the first analyte introduced into the main separation column 32 is separated into individual gas phase components in the main separation column 32, and the separated individual gas phase components are separated. is detected by the detection means 41, a total ion chromatogram (TIC) shown in the upper part of FIG. 4 can be obtained.

The total ion chromatogram (TIC) shown in the upper part of FIG. 4 is the total ion chromatogram (TIC) of the components including Irgaphos 168 etc. as the additive contained in EVA as the polymer material in a free state. . In addition, an extracted ion chromatogram (EIC) of oxidized Irgaphos 168 with m/z 647 from libraries such as various databases is shown in the lower part of FIG.

From FIG. 4 , among the components obtained by thermal desorption of EVA, the peak with a retention time of about 24 minutes can be identified as oxidized Irgaphos 168 .

In the method for analyzing a polymeric material of this embodiment, after the analysis of the first component to be analyzed is completed, helium, The heating furnace 21 is heated to a predetermined temperature, for example, 600° C. by the heater 22 while a carrier gas such as nitrogen is supplied to the heating furnace 21 at a flow rate of, for example, 200 ml/min. Next, while the suction pump 5 is in operation, the polymer material, which has been evacuated while being accommodated in the sample cup 6, is put into the heating furnace 21 as a sample, and the polymer material itself is instantaneously thermally decomposed. to produce a second gas phase component mixture.

At this time, in the method for analyzing a polymeric material according to the present embodiment, the split vent 35 is opened, so that the generated second gas phase component mixture is partially split according to a predetermined split ratio by the split vent 35. is introduced into the pre-column 31, while the remainder is discharged to the outside.

At this time, the temperature of the pre-column 31 is set to, for example, 40° C., and among the components contained in the second gas phase component mixture, the component having a boiling point of over 40° C. is the second component to be analyzed. Trapped at 31. On the other hand, among the components contained in the second gas phase component mixture, components with a boiling point of 40° C. or less are sucked by the suction pump 5 and discharged to the outside as non-analytical components. When the second gas phase component mixture contains a large amount of a solvent or the like, most of the solvent or the like has a boiling point of 40° C. or less, so most of it is discharged to the outside as the non-analyte component. .

Next, when the second analyte component is trapped in the pre-column 31, the suction pump 5 is stopped, the pre-column 31 is heated to a temperature at which the second analyte component can be vaporized, and the second analyte component is Vaporize the analyte. Specifically, the operation of heating the pre-column 31 to a temperature at which the second component to be analyzed can be vaporized is performed by raising the temperature of the constant temperature bath 3 . For example, the temperature of the constant temperature bath 3 is maintained at 40° C. for 2 minutes, the temperature is raised from 40° C. to 320° C. at a rate of 20° C./min, and held at 320° C. for 14 minutes to obtain the second analyte component. is vaporized and the vaporized second analyte is introduced into main separation column 32 via three-way tube 33 . Since the main separation column 32 is a separation column, the second analyte introduced into the main separation column 32 is separated into individual gas phase components in the main separation column 32, and the separated individual gas phase components are separated. is detected by the detection means 41, a pyrogram of the components constituting the polymer material itself shown in FIG. 5 can be obtained.

As a result, according to the method for analyzing a polymeric material of the present embodiment, when analyzing a polymeric material by the double-shot method using the gas phase component analyzer 1 shown in FIG. Thus, without changing the split ratio of the gas phase component analyzer 1, information on both components such as additives contained in the polymer material in a free state and the components of the polymer material itself can be obtained. can be reliably obtained.

DESCRIPTION OF SYMBOLS 1, 11... Gas phase component analyzer 2... Heating means 3... Constant temperature bath 4... Detection means 5... Suction means 31... First column 32... Second column 33... Connection means 35... Divided introduction means 36...Selective introduction means 40...Metal tube with inert inner surface.

Claims (2)

A heating means for heating a sample to generate a gas phase component mixture, a first column into which the gas phase component mixture generated by the heating means is introduced, and a note connecting the heating means and the first column. an inlet, a second column which is a separation column connected to the first column via connecting means, a constant temperature bath containing the first column, the second column and the connecting means; detecting means for detecting individual gas phase components separated by said second column; suction means connected to said connecting means; said gas phase component mixture provided in said inlet and generated by said heating means while introducing a part of the gas phase component mixture into the first separation column while discharging the rest to the outside; A method for analyzing a polymeric material using a gas phase component analyzer equipped with a selective introduction means for introducing into and discharging the remainder to the outside,
selecting a temperature range in which the first analyte component is generated from the results of evolved gas analysis of the sample;
The sample is heated in the heating means while the selective introduction means and the suction means are operated, and the components contained in the sample in a free state are thermally desorbed from the sample, and the first producing a gas phase component mixture, and selectively introducing the first gas phase component mixture produced in a temperature range in which the first analyte occurs into the first column through the inlet; capturing on the first column a first analyte contained in the first gas phase mixture of components;
After capturing the first analyte in the first column, the selective introduction means and the suction means are stopped, and the first column is brought to a temperature at which the first analyte is vaporizable. heating to vaporize the first analyte;
a step of introducing the vaporized first analyte component into the second column, separating it into individual gas phase components, and detecting the separated individual gas phase components with the detection means;
The sample is heated in the heating means after the component contained in the free state is thermally desorbed, while the divided introduction means is opened, the selective introduction means is stopped, and the suction means is operated. and pyrolyzing the sample to produce a second gas phase component mixture;
Part of the generated second gas phase component mixture is introduced into the first column by the divided introduction means, while the remainder of the second gas phase component mixture is discharged to the outside, and the second gas phase component mixture is discharged to the first column. capturing on the first column a second analyte contained in the second gas phase mixture of components introduced into the first column;
After capturing the second analyte component in the first column, the suction means is stopped, the first column is heated to a temperature at which the second analyte component can be vaporized, and the second analyte component is a step of vaporizing the analyte component of
introducing the vaporized second analyte component into the second column, separating it into individual gas phase components, and detecting the separated individual gas phase components with the detection means. A method for analyzing polymeric materials characterized by: 2. The method for analyzing a polymer material according to claim 1, wherein said generated gas analysis method comprises a metal column whose inner surface is inactivated instead of said first column and said second column of said gas phase component analyzer. A method for analyzing a polymer material, characterized by using a tube.

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