Polymer sample analyzer

Abstract

To provide a polymer sample analyzer capable of reducing a frequency of occurrence of an abnormality peak in a pyrogram.SOLUTION: A polymer sample analyzer includes: a gas phase component generating device 10; a first column 21 connected to the gas phase component generating device 10 via an introduction part and configured to introduce a gas phase component mixture generated from a sample at the gas phase component generating device; a second column 21 connected at an introduction port thereof only to a discharge port of the first column 21 and configured to separate the gas phase component mixture to each gas phase component; a thermostatic bath 20 housing the first column 21 and the second column 22; and a detector 40 connected to the discharge port of the second column 22 and configured to detect each gas phase component separated at the second column 22. No liquid phase is present inside the first column 21.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polymer sample analyzer for analyzing polymer samples such as plastics. [Background technology]

[0002] Conventionally, for example, as shown in FIG. 11, a polymer sample analyzer (gas phase component analyzer (gas chromatograph)) has been known that includes a gas phase component generator 10, a thermostatic chamber 20, and a detector 40 (see, for example, Patent Document 1).

[0003] The gaseous component generator 10 (pyrolyzer) generates a gaseous component mixture by heating a polymer sample to pyrolyze or volatilize the sample, or by heating the sample to thermally desorb components contained in the sample. An inert gas such as He is supplied as a carrier gas from a carrier gas source (not shown) to the gaseous component generator 10 through a carrier gas supply line L1. The thermostatic bath 20 (oven) houses a separation column 22. The separation column 22 has an inlet connected to the gaseous component generator 10 via an inlet 12 and separates the gaseous component mixture generated in the gaseous component generator 10 and carried by the carrier gas into individual gaseous components. A split vent L2 connected to the inlet 12 introduces a portion (e.g., 1-10%) of the gaseous component mixture into the separation column 22, while the remainder (e.g., 90-99%) is discharged to the outside. The detector 40 is connected to the outlet of the separation column 22 and detects the individual gas phase components separated in the separation column 22. The detector 40 is configured by, for example, a mass spectrometry detector (MS).

[0004] According to the polymer sample analyzing apparatus having this configuration, as shown in FIG. 12, the temperature Θ 20 (Furthermore, the temperature Θ of the separation column 22 22 During the process of gradually increasing the temperature from 40° C. (held for 2 minutes) to 20° C. / minute to 300° C., a pyrogram is obtained as a result of detection of gas phase components by detector 40. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 5087564 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0006] However, as shown in Figure 12, for example, the peak of a low-boiling component (e.g., C10') in a pyrogram is a normal peak with a sharp, symmetrical shape, while the peak of an intermediate-boiling component (e.g., C20') is an abnormal peak with a slow rising shape. Furthermore, the relatively large or high main peak of a high-boiling component (e.g., C30') is a normal peak with a symmetrical shape, but the lower right of Figure 12 shows the presence of several small abnormal peaks on the rising side of the peak, enclosed by a two-dot chain line. The lower left of Figure 12 shows an enlarged view of the intermediate-boiling component peak in the pyrogram, and it can be seen that the base of the rising side, enclosed by a one-dot chain line, is significantly raised. The presence of such abnormal peaks can significantly reduce the accuracy of sample identification and quantification.

[0007] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a polymer sample analyzer that can reduce the frequency of abnormal peaks appearing in a pyrogram. [Means for solving the problem]

[0008] The present inventors have considered the mechanism by which abnormal peaks appear in pyrograms as described above and have hypothesized that it may be due to the mechanism shown in Figures 13A to 13E. Figures 13A to 13E show simulated time-series distributions of low-boiling-point components (e.g., see the C10' / white distribution map), intermediate-boiling-point components (e.g., see the C20' / gray distribution map), and high-boiling-point components (e.g., see the C30' / black distribution map) in the internal space of separation column 22.

[0009] The left side of Figure 13A shows the temperature profile from the gaseous component generator 10 through the inlet and outlet of the separation column 22 via the inlet 12, immediately after the gaseous component mixture generated from the sample is introduced from the gaseous component generator 10 into the inlet 12. At this stage, the temperature Θ 20 The temperature Θ of the gas phase component generator 10 is controlled to 40°C. 10 The temperature Θ of the introduction part 12 (ambient temperature of the sample) is controlled to 600°C. 12 is controlled at 300°C.

[0010] As shown in Figure 13A, ideally, the low-, medium-, and high-boiling components produced by pyrolysis at 600°C are introduced into the internal space of the separation column 22 at approximately the same time. However, about 10% of these pyrolysis components are introduced slightly before the main pyrolysis component, and do not form a pulse-like narrow introduction bandwidth. Here, the low-boiling components are introduced relatively normally (in an approximately normal distribution with small variance) with a pulse-like bandwidth, but the medium- and high-boiling components are introduced at a temperature Θ near the inlet of the separation column 22. 22 Because their boiling points are relatively low, they are temporarily collected in a cold trap. However, because the intermediate-boiling and high-boiling components have different boiling points, they are introduced into the separation column 22 later than the low-boiling components, rather than instantaneously. If this introduction is not instantaneous, the component peaks will become abnormal peaks. In particular, if some of the intermediate-boiling components enter the separation column early or late, this can cause abnormal peaks.

[0011] As shown in FIG. 13B, the temperature Θ of the thermostatic chamber 20 20 During the temperature control process until the temperature reaches 80°C, the low boiling point components move toward the outlet of the separation column 22 while repeatedly slightly distributing with the liquid phase 220 present inside the separation column 22. During this process, the intermediate boiling point components move toward the outlet of the separation column 22 while the temperature Θ 22 During this process, the high boiling point components hardly move at all because they are less volatile and are retained in the liquid phase of the separation column.

[0012] As shown in FIG. 13C, the temperature Θ of the thermostatic chamber 20 20 Even during the process of further temperature control until the temperature reaches 150°C, the low boiling point components move toward the outlet of the separation column 22 while repeatedly distributing slightly with the liquid phase 220 present inside the separation column 22. During this process, the intermediate boiling point components continue to disperse at the temperature Θ 22 The components move further with the increase in temperature, and although their distribution is close to a normal distribution, the dispersion becomes larger, reflecting slight abnormal distribution of the components due to differences in the time of introduction into the inlet of the separation column 22. In particular, the small amount of intermediate boiling point components introduced first into the separation column 22 undergoes repeated distribution (dissolution-desorption) in the surface layer of the liquid phase, but because distribution is limited to the surface layer of the liquid phase, the component's progression speed is faster than that of the main high boiling point components shown next. In the case of the main intermediate boiling point components, the components penetrate relatively deep into the liquid phase, and then desorb into the spatial layer of the separation column according to the distribution law, and proceed to the outlet of the separation column while repeating this dissolution and desorption. The intermediate boiling point components introduced slightly earlier have a relatively high progression speed, and therefore exhibit an abnormal distribution P as shown in Figure 13C. M_irr , the abnormal distribution P as shown in Fig. 13D and Fig. 13E M_irr1 and P M_irr2 During this process, the high boiling point components hardly move.

[0013] As shown in FIG. 13D, the temperature Θ of the thermostatic chamber 20 20 The low boiling point components move to the detector 40 while the temperature of the separation column 22 is further controlled to rise to 250°C. 22 The higher the temperature, the more the distribution shifts, resulting in an asymmetric distribution and a larger dispersion. Some of the high boiling point components shift slightly, resulting in a two-peak distribution (abnormal distribution P H_irr has appeared).

[0014] As shown in FIG. 13E, the temperature Θ of the thermostatic chamber 20 20 is further heated to 3000°C, the intermediate boiling point components are heated to a temperature Θ 22The higher the temperature, the more the high boiling point components will shift, and the asymmetry of their distribution will increase, further increasing the dispersion. Although the high boiling point components generally shift, their distribution will become even more asymmetrical or distorted with three peaks, and the dispersion will also increase (abnormal distribution P M_irr1 and P M_irr2 has appeared).

[0015] It is presumed that the mechanism by which the abnormal peaks of the medium-boiling point components and the high-boiling point components appear in the pyrogram is that the distribution states of the medium-boiling point components and the high-boiling point components in the internal space of the separation column 22, as shown in Figures 13A to 13E, change over time due to the presence of the liquid phase 220 inside the distribution column 22.

[0016] Based on this assumption, the polymer sample analyzing device of the present invention is a gas phase component generator for heating a polymer sample as a sample to generate a gas phase component mixture; a first column having an inner surface not coated with a liquid phase, the first column being connected to the gas phase component generator via an inlet and into which the gas phase component mixture generated from the sample in the gas phase component generator is introduced; a second column having an inlet connected only to the outlet of the first column and having an inner surface coated with a liquid phase for separating the gaseous component mixture into individual gaseous components; a thermostatic chamber that accommodates the first column and the second column; a detector connected to an outlet of the second column and detecting individual gas phase components separated in the second column; and a control device for controlling the temperatures of the gas phase component generating device, the introduction section, and the thermostatic bath. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a simplified diagram illustrating the configuration of a polymer sample analyzer according to a first embodiment of the present invention. [Figure 2A] FIG. 1 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the first embodiment. [Figure 2B]FIG. 1 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the first embodiment. [Figure 2C] FIG. 1 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the first embodiment. [Figure 3] FIG. 2 is an exemplary view of a pyrogram of the polymer sample analyzer according to the first embodiment of the present invention. [Figure 4] FIG. 10 is a simplified explanatory diagram of the configuration of a polymer sample analyzer according to a second embodiment of the present invention. [Figure 5A] FIG. 10 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the second embodiment. [Figure 5B] FIG. 10 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the second embodiment. [Figure 5C] FIG. 10 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the second embodiment. [Figure 5D] FIG. 10 is an explanatory diagram illustrating the principle of the polymer sample analyzer of the second embodiment. [Figure 6] FIG. 10 is an exemplary view of a pyrogram of the polymer sample analyzer according to the second embodiment of the present invention. [Figure 7] FIG. 10 is an example of a pyrogram of a polymer sample analyzer according to a comparative example. [Figure 8A] FIG. 1 is an explanatory diagram of the peak separation effect when no packing material is used. [Figure 8B] FIG. 1 is an explanatory diagram of the peak separation effect when a packing material is present. [Figure 9] FIG. 1 is an explanatory diagram of the peak separation effect when no packing material is used. [Figure 10] FIG. 1 is an explanatory diagram of the peak separation effect of a packing material and a pre-column. [Figure 11] FIG. 1 is a simplified diagram illustrating the configuration of a polymer sample analyzer according to the prior art. [Figure 12] FIG. 1 is an exemplary diagram of a pyrogram of a polymer sample analyzer according to the prior art. [Figure 13A] FIG. 1 is an explanatory diagram illustrating the principle of a conventional polymer sample analyzer. [Figure 13B] FIG. 1 is an explanatory diagram illustrating the principle of a conventional polymer sample analyzer. [Figure 13C] FIG. 1 is an explanatory diagram illustrating the principle of a conventional polymer sample analyzer. [Figure 13D] FIG. 1 is an explanatory diagram illustrating the principle of a conventional polymer sample analyzer. [Figure 13E] FIG. 1 is an explanatory diagram illustrating the principle of a conventional polymer sample analyzer. DETAILED DESCRIPTION OF THE INVENTION

[0018] (First embodiment) The polymer sample analyzer (gas phase component analyzer (gas chromatograph)) according to the first embodiment of the present invention shown in FIG. 1 comprises a gas phase component generator 10, a thermostatic chamber 20, a detector 40, and a control device 200.

[0019] The gas phase component generator 10 (pyrolyzer) generates a gas phase component mixture by heating a polymer sample to pyrolyze or volatilize the sample, or by heating the sample to thermally desorb components contained in the sample. The gas phase component generator 10 includes a heating furnace 101 made of a chemically inert, approximately cylindrical quartz tube, a first heater 102 provided around the heating furnace 101, and an introduction section 12 (GC introduction section) into which the tip of the heating furnace 101 is inserted. The introduction section 12 includes a second heater 122.

[0020] The heating furnace 101 is connected to the upper part of the introduction part 12 via a heated pipe, or is itself detachably attached to the upper part of the introduction part 12 without using a pipe or the like. The heating furnace 101 may be configured as a stainless steel tube, instead of a quartz tube, which is inactivated by forming a thin quartz film on the inner surface thereof.

[0021] The gas phase component generation device 10 is equipped with a sample introduction section (not shown) connected above the heating furnace 101. A carrier gas supply line L1, which introduces a carrier gas from a carrier gas source CGS into the heating furnace 101, is connected to the sample introduction section. A flow rate control device is provided in the carrier gas supply line L1.

[0022] The polymer sample analyzer is equipped with a split vent L2 that can be opened and closed by a valve (not shown). When split vent L2 is open, it introduces a portion of the gaseous component mixture introduced from pyrolysis furnace 101 to inlet 12 into first column 21, while discharging the remainder to the outside. In split vent L2, the split ratio, which is the ratio of the components introduced into first column 21 to the total amount of the gaseous component mixture, is set to a predetermined value (for example, 1 / 100 to 1 / 10).

[0023] The thermostatic bath 20 (oven) accommodates a first column 21 (pre-column) and a second column 22 (separation column). The thermostatic bath 20 is equipped with a thermostatic bath heater 202.

[0024] The inlet of first column 21 is detachably connected to inlet 12 of gas phase component generator 10, and its outlet is detachably connected only to the inlet of second column 22 via connector 24. The inner surface of first column 21 is chemically inert. As first column 21, for example, a stainless steel or fused silica capillary column having an inner diameter of 0.1 to 0.5 mm and a length of 0.5 to 10 m and no fixed layer (liquid phase 220) inside is used.

[0025] The second column 22 has an inlet connected only to the outlet of the first column 21 via a connection 24 (e.g., a two-way tube or two-way connector), and the outlet is connected to the detector 40. A liquid phase 220 (polymer) is provided inside the second column 22 (see Figures 3A to 3C), and separates the gaseous component mixture carried by the carrier gas from the heating furnace 101 via the inlet 12 and the first column 21 into individual gaseous components. The inner surface of the second column 22 is chemically active. The second column 22 may be, for example, a stainless steel or fused quartz capillary column with an inner diameter of 0.1 to 0.5 mm, a length of 30 m, and a 0.25 μm-thick stationary layer (liquid phase 220) made of a copolymer of diphenylpolysiloxane and dimethylpolysiloxane in a molar ratio of 5:95.

[0026] The detector 40 is connected to the outlet of the second column 22 and detects the individual gas phase components separated by the second column 22. The detector 40 is composed of a mass spectrometer (MS) such as a quadrupole mass spectrometer detector, a flame ionization detector (FID), an electron capture detector (ECD), or the like.

[0027] (function) In the polymer sample analyzing apparatus having this configuration, the operation of the first heater 102 is controlled by the control device 200, so that the temperature Θ 10 The temperature of the heating furnace 101 is controlled to be in a first temperature range of 40°C to 1150°C (for example, 600°C). The controller 200 controls the operation of the second heater 102, thereby controlling the temperature Θ of the introduction section 12. 12 is controlled to be in a second temperature range of room temperature to 450°C (for example, 300°C). The controller 200 controls the operation of the constant temperature bath heater 202, so that the temperature Θ of the constant temperature bath 20 20 (Furthermore, the temperature Θ of the first column 21 21 and the temperature Θ of the second column 22 22 ) is controlled to increase from a temperature lower than the lower limit of the second temperature range to a temperature included in the second temperature range.

[0028] For example, the temperature Θ of the thermostatic chamber 20 20 (Furthermore, the temperature Θ of the separation column 22 22 The temperature is controlled so that it gradually rises from 40°C (held for 2 minutes) to 300°C at a rate of 20°C per minute. During this process, a pyrogram is obtained as a result of detection of gas phase components by detector 40. During this time, split vent L2 is steadily maintained in an open state (split ratio, for example, 1 / 50).

[0029] Figures 2A to 2C show simulated time-series distributions of low-boiling point components (e.g., C1' to C15' / see white distribution diagram), medium-boiling point components (e.g., C16' to C30' / see gray distribution diagram), and high-boiling point components (e.g., C31' and above / see black distribution diagram) in the internal space of separation column 22.

[0030] 2A shows the temperature profile from the gaseous component generator 10 through the inlet and outlet of the first column 21, and further from the inlet and outlet of the second column 22, immediately after the gaseous component mixture generated from the sample is introduced from the gaseous component generator 10 into the inlet 12. At this stage, the temperature Θ 20 The temperature Θ of the gas phase component generator 10 is controlled to 40°C. 10 The temperature Θ of the introduction part 12 (ambient temperature of the sample) is controlled to 600°C. 12 is controlled at 300°C.

[0031] 2A, the low-boiling component, the intermediate-boiling component, and the high-boiling component are ideally introduced into the internal space of the first column 21 at approximately the same time. 21 Because the temperature is relatively low, the progress of each boiling point component to the outlet is temporarily stagnated (cold trapped). Here, there is no liquid phase in the first column 21, and equilibrium distribution does not occur. Therefore, the low-, medium-, and high-boiling components overlap, but their bandwidths are narrow. Among them, the medium-boiling components have volatility intermediate between the low- and high-boiling components, so as shown in Figure 13C, there is a time difference between the components introduced first into the second column 22 and those introduced later into the second column 22.

[0032] As shown in FIG. 2B, the temperature Θ of the thermostatic chamber 20 20 As the temperature of the first column 22 is controlled to reach 80°C, the bandwidth of the low-boiling components widens due to diffusion into the carrier gas, and they reach the second column 22. When the low-boiling components reach the second column 22, they repeatedly distribute with the liquid phase 220 present inside the second column 22, and the forward speed temporarily stagnates due to distribution equilibrium at the front end of the liquid phase of the second column 22, so the bandwidth narrows. Then, they move toward the outlet of the second column 22 while maintaining a normal distribution state. During this process, the intermediate-boiling and high-boiling components move away from the first column 21 at the temperature Θ 21As the temperature rises, the bandwidth of the low-boiling components in the internal space of the first column 21 widens due to diffusion into the carrier gas, but they move while maintaining an abnormal distribution state.

[0033] As shown in FIG. 2C, the low boiling point components are heated to a temperature Θ 20 is further heated and controlled until it reaches 250°C, it repeatedly distributes with the liquid phase 220 present inside the second column 22, and moves toward the outlet of the second column 22 while maintaining a normal distribution state. 22 When the gas reaches the liquid phase 220 inside the second column 22, the gas is concentrated by partitioning with the liquid phase 220, narrowing the bandwidth. The gas then moves toward the outlet of the second column 22 while maintaining a narrow, normal distribution (a nearly normal distribution with a small variance).

[0034] As shown in Figure 3, the peaks of low-boiling components (e.g., C1' to C15'), medium-boiling components (e.g., C16' to C30'), and high-boiling components (e.g., C31' and above) in the pyrogram are normal peaks with sharp, nearly symmetrical shapes. In other words, the appearance of abnormal peaks is suppressed.

[0035] Even if the medium-boiling point components and high-boiling point components have abnormal distributions in the first column 21 as shown in Figures 2A and 2B, it is presumed that the mechanism by which the appearance of abnormal peaks is suppressed is that they reach the separation column and are concentrated.

[0036] (Second embodiment) The polymer sample analyzer (gas-phase component analyzer (gas chromatograph)) according to a second embodiment of the present invention, shown in FIG. 4, further includes a packing material f (e.g., 40- to 60-mesh diatomaceous earth particles with a deactivated surface) packed into the inlet 12. A breathable retaining member w (e.g., quartz wool) is provided on both the upstream and downstream sides of the packing material f to retain the packing material f. The packing material f may be deactivated quartz particles, a deactivated porous GC packing material (e.g., Chromosorb porous polymer adsorbent ("Chromosorb" is a registered trademark)), an insert tube packed with quartz wool only at a high density (e.g., higher density than the retaining member w), or alpha alumina particles. The other components of the polymer sample analyzer of the second embodiment are substantially similar to those of the polymer sample analyzer of the first embodiment, and therefore, the same components are designated by the same reference numerals and will not be described again.

[0037] (function) The operation of the polymer sample analyzer having this configuration is substantially the same as that of Embodiment 1. Figures 5A to 5D show simulated time-series distributions of low-boiling-point components (e.g., C1' to C15' / see white circles), intermediate-boiling-point components (e.g., C16' to C30' / see gray circles), and high-boiling-point components (e.g., C31' and above / see black circles) in the internal space of separation column 22.

[0038] 0.3 mg of high density polyethylene (HDPE) was used as a sample. 10 (ambient temperature of the sample) was controlled at 600°C. The temperature Θ of the introduction part 12 12 The temperature Θ of the thermostatic bath 20 was controlled to 300°C. The second column 22 was, for example, a stainless steel capillary column having an inner diameter of 0.25 mm, a length of 30 m, and a 0.25 μm thick fixed layer (liquid phase 220) inside, which was made of a copolymer of diphenylpolysiloxane and dimethylpolysiloxane in a molar ratio of 5:95. 20 The temperature was maintained at 40°C for 2 minutes and then controlled to increase to 320°C in 20 minutes.

[0039] A polymer placed in a sample cup 104 (for example, made of stainless steel with an inner diameter of 4 mm and a height of 8 mm) placed upstream of the heating furnace 101 is heated to Θ 10 The pyrolysis occurs instantaneously within one second in a temperature environment of 600°C. The pyrolysis product is a mixture of low-boiling-point components, medium-boiling-point components, and high-boiling-point components that are mixed almost uniformly. The temperature Θ at the downstream part of the heating furnace 101 (the part of the heating furnace 101 that connects to the inlet part 12) 10 The temperature Θ′ is about 300°C, which is lower by about 300°C than that of the upstream part of the heating furnace 101. For this reason, the pyrolysis products introduced from the upstream part to the downstream part of the heating furnace 101 are distributed in the order of low boiling point components (see white circles), medium boiling point components (see gray circles), and high boiling point components (see black circles) from the downstream side, as shown schematically in FIG. 5A, but are in a non-uniform mixed state. The temperature of the pyrolysis components is higher than the temperature Θ 10 = 600°C, the temperature Θ 10 '=It is at a temperature higher than 300°C.

[0040] Next, the heterogeneously mixed pyrolysis product is introduced into the inlet 12 (GC injection port) from the downstream portion of the heating furnace 101 or a needle (not shown). The pyrolysis product is introduced into a glass tube (e.g., 4 mm inner diameter) that constitutes the inlet 12 or is located within its internal space, and proceeds toward the inlet of the first column 21. During this process, the individual boiling point components of the pyrolysis product travel through the voids of the packing material f while being randomly diffused and mixed with the carrier gas. As shown schematically in Figure 5B, the pyrolysis product exchanges heat with the packing material f maintained at 300 °C, and its temperature drops and condenses in a short time, narrowing its distribution width. Furthermore, as shown schematically in Figure 5B, the low-, medium-, and high-boiling point components of the pyrolysis product are homogenized as they travel through the voids of the packing material f.

[0041] Next, the thermal decomposition product is introduced into the first column 21 from the connection (inlet insert tube) between the inlet 12 and the first column 21. 20The temperature is controlled to 40°C. Therefore, as shown schematically in FIG. 5C, high-boiling components are cold trapped near the inlet of the first column 21, significantly slowing their progression speed. Meanwhile, although the intermediate-boiling components slow their progression speed in the first column 21, they progress faster than the high-boiling components, with some of these components (abnormal components) progressing relatively faster than the other components. As a result, as shown schematically in FIG. 5C, the distribution ranges of high-boiling components and intermediate-boiling components are clearly separated in the first column 21, and the distribution width of the intermediate-boiling components is slightly wider due to the presence of the abnormal components. As shown schematically in FIG. 5C, low-boiling components are hardly cold trapped in the first column 21 and flow into the second column 22 along with the carrier gas. Because the low-boiling components have a small distribution coefficient with the liquid phase of the second column 22 (separation column), they progress through the internal space of the second column 22 without being significantly slowed down by the carrier gas.

[0042] Next, as shown schematically in Figure 5D, the intermediate boiling point components (see gray circles) are released at Θ 22 At a temperature of 40°C in the second column 22, the intermediate-boiling components are cold trapped near the inlet of the second column 22, slowing their rate of progression. Then, some of the intermediate-boiling components (abnormal components) that progressed relatively quickly in the first column 21 narrow their distribution width and become sharply distributed due to the concentration effect of the liquid phase 220 distributed near the inlet of the second column 22. As a result, the distribution ranges of the low-boiling, intermediate-boiling, and high-boiling components are clearly separated, and abnormal peaks in the distribution of the intermediate-boiling components in particular are reduced.

[0043] As shown in Figure 6, the peaks of the low-boiling components (e.g., C1' to C15'), the intermediate-boiling components (e.g., C16' to C30'), and the high-boiling components (e.g., C31' and above) in the pyrogram are normal peaks with sharp, nearly symmetrical shapes. In other words, the abnormal peaks have almost disappeared.

[0044] 7 shows a pyrogram obtained using a comparative polymer sample analyzer that does not include packing material f and first column 21. In this pyrogram, the peaks of intermediate-boiling components (e.g., C16' to C30') are asymmetric and somewhat broad, and the presence of abnormal peaks is observed. Therefore, it can be seen that the heights of the peaks of intermediate-boiling components in the pyrogram of FIG. 7 vary more than in the pyrogram of FIG. 6.

[0045] FIG. 8A shows the relationship between the length of the first column 21 and the peak C in the extracted ion chromatogram (EIC) of mass m / z 82 when the filler f is not provided in the inlet 12 according to the first embodiment. x ' and C x The relationship between the degree of separation (x=16, 18, 20, 21) and is shown.

[0046] From FIG. 8A, in the region where the length of the first column 21 is about 2 m, peak C in the extracted ion chromatogram (EIC) of mass m / z 82 x ' and C x It can be seen that the resolution of " (x = 16, 18, 20, 21) shows the maximum value. Furthermore, from FIG. 8A, in the region where the length of the first column 21 is about 0.25 m, peak C in the extracted ion chromatogram (EIC) of mass m / z 82 x ' and C x It can be seen that the separation degree for all of the " (x = 16, 18, 20, 21) is significantly reduced. This is because the first column 21 is too short, and the linear velocity of the intermediate boiling point components (e.g., C16" and C16') present in the carrier gas, such as He gas, drops sharply from 0.67 m / s to 0.25 m / s in the introduction section 12, causing the intermediate boiling point components present in the inert gas at the outlet of the introduction section 12 to become more non-uniform. It can be assumed that the high boiling point components also behave in a similar manner. From this perspective, it is preferable that the length of the first column 21 be 1.0 m or more.

[0047] FIG. 8B shows the relationship between the length of the first column 21 and the peak C in the extracted ion chromatogram (EIC) of mass m / z 82 when the inlet 12 is filled with filler f and the first column 21 is further provided according to the second embodiment. x ' and C x The relationship between the resolution of the peak C in the EIC and the resolution of the peak C in the EIC (x=16, 18, 20, 21) is shown in Fig. 8B, compared to Fig. 8A, with the change in the length of the first column 21. x ' and C x There is no significant variation in the degree of separation of ". This indicates that it is important that the pyrolysis components form a nearly uniformly mixed band in the introduction section 12, and that this state is maintained while the small abnormal agglomerates are homogenized with the carrier gas as they pass through the first column 21 and reach the second column 22. This confirms that the best peak area reproducibility is achieved by simultaneously using the packing material f and the first column 21 having a length of 2 to 4 m in accordance with the second embodiment (see C21" in Figure 10).

[0048] FIG. 9 shows the peak C in the extracted ion chromatogram (EIC) of mass m / z 82 when the length of the first column 21 is 0 m, 2 m, and 8 m. x ' and C x ”(x=16, 21) is shown.

[0049] From the left side of Figure 9, peak C 16 ' and C 16 When the length of the first column 21 is 0 m, the width of these peaks is wider than when it is 2 m, which shows that the molecules are widely diffused in the direction of travel. When the length of the first column 21 is 2 m or 8 m, the width of peak C is wider than when the length of the first column 21 is 0 m. 16 ' and C 16 From the right side of Figure 9, peak C 21 ' and C 21The width of each peak of " " is wider when the length of the first column 21 is 0 m than when the length of the first column 21 is 2 m, which indicates that the molecules are widely diffused in the direction of travel. When the length of the first column 21 is 2 m, the molecules are clearly separated compared to when the length of the first column 21 is 0 m. On the other hand, when the length of the first column 21 is 8 m, the peak C 21 ' and C 21 This indicates that, since the liquid phase 220 is not applied to the inner surface of the first column 21, the longer the length of the first column 21, the more the boiling point components diffuse in the traveling direction.

[0050] FIG. 10 shows the relationship between the presence or absence of the packing material f and the first column 21 and the peak C in the total ion current chromatogram (TIC). 21 , C 21 ' and C 21 " and peak C in the extracted ion chromatogram (EIC) of mass m / z 82. 21 ' and C 21 " and peak C in the TIC 21 and C 21 ' and peak C in the EIC 21 The relative standard deviation of the area values ​​of "C" obtained from four consecutive measurements 21 The RSD% of the peak area values ​​of " and " are shown.

[0051] In the comparative example in which neither the filler f nor the first column 21 was present, the resolution was 0.47. 21 The relative standard deviation of the peak area values ​​of " was 7.57%. In the reference example in which the packing material f was present but the first column 21 was not present, the resolution was 0.77, and the C 21 The relative standard deviation of the peak area values ​​of " was 3.33%. In Example 1, in which the first column 21 was present according to the first embodiment but the packing material f was not present, the resolution was 0.56, which was higher than that of the comparative example. 21The relative standard deviation of the peak area values ​​of " is 4.45%, which is lower than that of the comparative example. In Example 2 in which the packing material f and the first column 21 are both present according to the second embodiment, the resolution is 0.79, which is higher than that of Example 1, and the C 21 The relative standard deviation of the peak area values ​​of " was 0.68%, which is lower than that of Example 1.

[0052] From the above, the pyrolysis components are uniformly mixed with a carrier gas such as He gas in the introduction section 12, whose internal space is filled with packing material f. However, it was found that there are small molecular clusters of the anomalous component that precede the anomalous component, which result in an anomalous peak. Therefore, the molecular clusters of the preceding anomalous component are passed through a first column 21 of an appropriate length to further homogenize the molecular flow. Then, the initial molecular clusters of the anomalous component are dissolved and distributed in the liquid phase 220 of the second column 22, thereby slowing their progress. Next, almost all of the subsequent components reach the liquid phase 220 and combine with the molecular clusters of the initial anomalous component to form a single component. [Explanation of symbols]

[0053] 10. Gas phase component generator (pyrolyzer) 101‥Heating furnace 102‥1st heater 12‥Introduction part (GC introduction part) 122‥Second heater 20. Thermostatic bath (oven) 21. Column 1 22. Second column (separation column) 200...Control device 202‥Thermostatic oven heater 220‥Liquid phase 40. Detector CGS - Carrier gas source L1: Carrier gas supply line L2...Split vent.

Claims

1. a gas phase component generator for heating a polymer sample as a sample to generate a gas phase component mixture; a first column having an inner surface not coated with a liquid phase, the first column being connected to the gas phase component generator via an inlet and into which the gas phase component mixture generated from the sample in the gas phase component generator is introduced; a second column having an inlet connected only to the outlet of the first column and having an inner surface coated with a liquid phase for separating the gaseous component mixture into individual gaseous components; a thermostatic bath that accommodates the first column and the second column; a detector connected to an outlet of the second column and detecting individual gas phase components separated in the second column; a control device for controlling the temperatures of the gas phase component generator, the introduction section, and the thermostatic bath, Polymer sample analyzer.

2. 2. The polymer sample analyzer according to claim 1, The introduction section is provided with a filler. Polymer sample analyzer.

3. 3. The polymer sample analyzer according to claim 1, The control device controlling the temperature of the gas phase component generator within a first temperature range of 40°C to 1150°C; controlling the temperature of the introduction section within a second temperature range of room temperature to 450°C; The temperature of the thermostatic chamber is controlled so as to increase from a temperature lower than the lower limit of the second temperature range to a temperature included in the second temperature range. Polymer sample analyzer.

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