JP6153108B2 - Volatile decomposition component collection and recovery device, liquid chromatograph, and volatile decomposition component analysis method - Google Patents

Description

  The present invention relates to a volatile decomposition component collection / recovery device that can also analyze volatile decomposition components that have been difficult to analyze by a conventional gas chromatograph (GC), and a liquid chromatograph (LC) and a volatile decomposition component analysis method using the same. About.

  In order to develop high-performance and high-performance materials using resin materials (polymer materials), it is necessary to clarify the fine chemical structure and component composition. Furthermore, there is a high demand for air purification indoors and vehicle interiors, and in addition to the removal of suspended matters such as fine dust, dust, bacteria and viruses, volatile organics that can be released from various resin materials (polymer materials) There is a need to analyze compounds (Volatile Organic Compounds: VOC) and the like with high accuracy.

  Conventionally, a gas chromatograph (GC) in which a volatile decomposition component, which is a product generated by heating a sample object, is detected by a detector while being separated by a column has been used for such analysis. It was. GC is widely used in various fields as an excellent analysis method for polymer materials, not limited to VOC analysis. For example, Patent Document 1 below describes such a GC.

  However, in GC, since it can be analyzed only by a volatile decomposition component carried by a carrier gas which is a mobile phase, a liquid is used for the mobile phase (high speed) liquid chromatograph (HPLC) when analyzing other components. Is used. The description regarding such GC exists in the following patent document 2, for example.

JP-A-5-346424 JP-A-5-157743

  Most generally, the polymer material (resin material) is often analyzed by GC rather than HPLC. However, when a polymer material or the like is pyrolyzed and analyzed by GC, even if a vapor phase volatile decomposition component is initially generated from a sample heated to about 500 to 600 ° C., the volatile decomposition component is not connected to piping such as a column. Since the temperature drops to about 300 to 400 ° C. when passing through, a part of the temperature is liquefied or solidified and is not detected. As a result, conventional GCs have not been able to effectively detect and analyze components such as high boiling points, high molecular weights, and high polarities that are likely to have useful structural information about the sample. Under such circumstances, it is not possible to effectively analyze high-performance advanced polymer materials that require the elucidation of the fine chemical structure at the molecular level.

  The present invention has been made in view of such circumstances, and is a liquid chromatograph that enables analysis of almost all products generated from a sample, including high-boiling components that have been difficult to analyze by conventional GC. It is an object of the present invention to provide a graph, a volatile decomposition component collection / recovery device used therefor, and a volatile decomposition component analysis method using the same.

  As a result of extensive research and trial and error, the present inventor has conducted high-volatility low-boiling components, etc. (referred to as “volatile components” as appropriate) among products generated by heating the sample. Is collected and recovered as it is, and low-volatile high-boiling components, etc. (this is referred to as “hard-volatile components” as appropriate) are temporarily attached (aggregated, adhered, adsorbed, etc.) to the inner wall surface. Incorporated) and then collected, and after that it was dissolved in a solvent and recovered. When this was actually tested, it was successful in analyzing almost all the products resulting from the polymer material (sample). By developing this result, the present invention described below has been completed.

《Volatile decomposition component collection and recovery device》
A volatile decomposition component collection / recovery device of the present invention includes a sample holder that holds a sample in a gas flow path into which a carrier gas flows and has a downstream end from which the volatile decomposition component generated from the sample and the carrier gas flow out. A heating means for heating the sample held in the sample holder; an upper opening detachably attached to the downstream end of the sample holder; an extension extending from the upper opening; and a downstream side of the extension comprising an induction deposition tube to be attached to or inner wall induces volatiles cracking component and a lower opening, and a first position and a switching valve which can switch between a second position in, said first position the extending portion of the induction attachment tube can be interpolated to the switching valve Ru is clamped by the downstream end portion of said sample holder openings on the said induction attachment tube when, in said second position said sample over the opening of the induction attachment tube when And is disengaged from the downstream end portion of the holder can be in communication over the opening of the induction attachment tube to the supply port for supplying the solvent for dissolving at least a portion of volatiles decomposition component adhering to the inner wall of the induction attachment tube It is characterized by that.

  When the volatile decomposition component collection / recovery device of the present invention is used, almost all of the volatile components and decomposition components (both referred to as “volatile decomposition components”) generated when the sample is heated can be effectively collected. The volatile decomposition components thus collected are dissolved in a solvent (mobile phase) and recovered, and then sent to a conventional liquid chromatograph (LC), particularly a high performance liquid chromatograph (HPLC), so that a conventional gas chromatograph ( It is possible to analyze not only low molecular weight, low boiling point or low polarity volatile components as analyzed in GC) but also high molecular weight, high boiling point or high polarity hardly volatile components (or decomposition components), etc. Become. In this way, it becomes possible to analyze a product having useful structural information with almost no leakage from samples made of various polymer materials.

  The operation of the volatile decomposition component collection and recovery apparatus of the present invention is as follows. First, the switching valve is set to the first position so that the upper opening of the guide attachment tube is attached to the downstream end of the sample holder. In this state, when the sample in the sample holder is heated by heating means, not only volatile components such as low molecular weight, low boiling point or low polarity but also low volatile components such as high molecular weight, high boiling point or high polarity, Generated from the sample. These are guided to the extension through the upper opening of the guide attachment tube from the downstream end of the sample holder.

  Here, even if the volatile component among the volatile decomposition components generated from the sample is cooled by the extending portion, the volatile component moves to the lower opening of the induction attachment tube by the carrier gas supplied from the upstream side of the sample holder. If bubbling (gas-liquid separation) or the like is performed by immersing in a solvent retention tank provided separately with the lower opening, the volatile component is dissolved in the solvent. In this way, volatile components are also collected and recovered in the solvent.

  However, of the volatile decomposition components generated from the sample, hardly volatile components adhere to the inner wall of the induction attachment tube due to a temperature drop while passing through the induction attachment tube, and do not move to the lower opening of the induction attachment tube. There are many cases. Therefore, as described above, after sufficiently collecting and collecting the volatile components, the upper opening of the guide attachment tube is separated from the downstream end of the sample holder, and the switching valve is set to the second position. And a solvent is supplied to the supply port of a switching valve from solvent supply means, such as a solvent tank provided separately. Then, the solvent is introduced into the induction attachment tube through the upper opening, and the hardly volatile component adhering to the inner wall is dissolved in the solvent and moves to the lower opening of the induction attachment tube. If this is introduced into the retention tank as described above, the hardly volatile component is also recovered. In this way, not only volatile components but also hardly volatile components are collected and recovered.

  If the collected material (solution in which the volatile decomposition components (thermal decomposition products) of the sample are dissolved in a solvent) is analyzed by HPLC, useful structural information that characterizes the sample that could not be analyzed by GC is also analyzed. become able to.

  In addition, you may consider the volatile decomposition component collection collection apparatus of this invention including the residence tank mentioned above and a solvent supply means. Further, the above-described attachment / detachment operation of the guide attachment tube according to the volatile decomposition component collection / recovery device of the present invention may be performed by an operator or automatically by a control device or the like.

《Liquid chromatograph》
The present invention is not limited to the above-described volatile decomposition component collection / recovery device, but can be grasped as a liquid chromatograph equipped with the device. In addition to the volatile decomposition component collection / recovery device described above, this liquid chromatograph is a pump that pumps out the solution by pumping out the solution from a retention tank containing a solvent (or solution) that dissolves the volatile decomposition component of the collected and recovered sample. It basically includes a loop injector, a column that separates volatile decomposition components into components when the pumped solution passes, and a detector that detects each component separated by the column.

<Method for analyzing volatile decomposition components>
The present invention can also be grasped as a volatile decomposition component analysis method using the liquid chromatograph. Furthermore, the present invention can be grasped not only as a liquid chromatograph (LC) but also as a volatile decomposition component analysis method using a gas chromatograph (GC) in combination. In this case, the present invention provides a gas analysis in which a gas chromatograph is used to analyze a volatile component derived from a lower opening of the induction attachment tube with the switching valve of the volatile decomposition component collection and recovery device described above being in the first position. And a liquid analysis step for analyzing the hardly volatile component dissolved in the solvent derived from the lower opening of the induction attachment tube by the liquid chromatograph by setting the switching valve to the second position after the gas analysis step. Can be grasped as a method for analyzing volatile decomposition components.

  The volatile component mentioned here can be analyzed by gas chromatography among the volatile decomposition components, and the hardly volatile component can be analyzed by liquid chromatography among the volatile decomposition components. Although both differ in terms of molecular weight, boiling point, polarity, etc., as long as the above-described volatile decomposition component collection and recovery apparatus is used, since both can be analyzed almost without omission, there is no need to clearly distinguish them.

  Even if the analysis step is separated in this way, as in the case described above, almost all products generated when the sample is heated can be analyzed without omission. Further, by using GC together, depending on the sample, it becomes possible to analyze volatile components with higher accuracy, and improvement in analysis capability can be expected.

It is a schematic diagram of the pyrolysis liquid chromatograph which is one Example concerning the present invention. It is sectional drawing explaining a mode that the attachment part vicinity of the sample holder and an induction | attachment attachment pipe | tube is gas-sealed. It is principal part sectional drawing which shows the state which made the three-way valve (switching valve) the 1st position. It is principal part sectional drawing which shows the state which made the three-way valve (switching valve) the 2nd position.

  The contents described in this specification can be applied not only to the volatile decomposition component collection and recovery apparatus of the present invention but also to a liquid chromatograph and an analysis method using the apparatus. One or two or more components arbitrarily selected from the present specification may be added to the above-described components of the present invention. Which embodiment is the best depends on the target, required performance, and the like.

《Volatile decomposition component collection and recovery device》
(1) Heating means The heating means according to the present invention may be of any kind or structure as long as the sample can be heated to a desired temperature. However, it is preferable to use a heating furnace that surrounds the sample holder because the sample can be stably heated at a desired constant temperature.

(2) Switching valve As long as the switching valve can be switched between the first position and the second position, the structure and form of the switching valve are not limited. It is preferable that the switching valve through which a solvent having a risk of ignition flows is provided separately from the heating means. Further, the switching valve is preferably provided with a means for preventing the solvent from flowing out to the heating means side (for example, a three-way valve) in the second position.

(3) Cooling means The volatile decomposition components generated from the sample are cooled when passing through the induction attachment tube, and a part of them adheres to the inner wall of the induction attachment tube. In order to manage or control the state of adhesion of the induction adhering tube to the inner wall, it is preferable to provide a temperature adjusting means capable of adjusting the temperature. As a simple structure, for example, a cooling means for cooling at least a part of the induction attachment pipe may be provided on the downstream side of the heating means. The cooling means may be of any type or structure, and for example, a cooler (air cooling fin, radiator), a fan, a water jacket, an electronic cooling element (Peltier), or the like can be used alone or in combination. In order to manage the carrier gas supplied to the sample holder, the temperature of the sample, etc., another cooling means may be provided on the upstream side of the heating means.

(4) Induction attachment tube The induction attachment tube has an upper opening that is detachable from the downstream end of the sample holder, and collects and collects volatile components (when the switching valve is in the first position). ) Arrangement (referred to as “first arrangement”) and arrangement (referred to as “second arrangement”) when collecting, extracting and collecting hardly volatile components (when the switching valve is in the second position). obtain.

  At this time, in order to prevent impurities and contaminants from entering the induction attachment tube, a shield tube is inserted between the downstream end of the sample holder and the upstream end of the switching valve to shield the induction attachment tube. preferable. By providing this shield tube, the induction attachment tube is held in a space cut off from the outside, and can be moved between the different arrangements described above while avoiding the entry of impurities and the like into the induction attachment tube.

  In addition, when the upper opening of the induction attachment tube is attached to the downstream end portion of the sample holder, it is preferable to seal the periphery of the attachment portion so that impurities and the like are not mixed from the outside. If a seal made of resin or rubber is used as the seal, volatile components generated from the seal may be mixed into the induction attachment tube. Therefore, it is preferable to use a gas seal as the seal.

  The gas seal can be performed by causing a seal gas to flow into the periphery of the installation portion (including cases where the gas is fed, jetted, or the like). The seal gas used is preferably the same component as the carrier gas for analysis. Further, the seal gas introduced to the periphery of the installation portion can not only seal only the installation portion but also flow into a cylindrical gap between the induction attachment tube and the shield tube externally attached thereto. Thereby, when the induction | attachment attachment pipe | tube moves to the 2nd arrangement | positioning from the above-mentioned 1st arrangement | positioning, it will be in the state sealed by gas, and it is preferable.

"Constitution"
A schematic diagram of a pyrolysis high-performance liquid chromatograph (Py-HPLC) 1 which is an embodiment according to the present invention is shown in FIG. The pyrolysis high-performance liquid chromatograph 1 (simply referred to as “chromatograph 1”) includes a volatile decomposition component collection / recovery device 2 and a high-performance liquid chromatograph (HPLC) 3. The high performance liquid chromatograph 3 is a known device including a pump 31, a loop injector 32, a separation column 33, and a detector 34, and detailed description thereof is omitted.

  The volatile decomposition component collection / recovery device 2 includes a cylindrical inlet 11 with a lid, a tubular sample holder 13 connected to the downstream side of the inlet 11, a heating furnace 14 (heating means) surrounding the sample holder 13, and An air cooling radiator 15 (cooling means) provided on the upstream side of the sample holder 13, a casing 12 surrounding the heating furnace 14 and the air cooling radiator 15, and an air cooling radiator provided on the lower outside of the casing 12. 16 (cooling means), an induction attachment pipe 17 extending downward from the downstream end 13a of the sample holder 13 through the air-cooling radiator 16, and a shield covering the upper outer peripheral surface by interpolating the induction attachment pipe 17 A pipe 18, a three-way valve 19 (switching valve) disposed at the lower end of the shield pipe 18, a solvent tank 21 for supplying a solvent m 1 to a supply port 191 (supply port) of the three-way valve 19, and an induction attachment pipe 17 The lower opening 17b is immersed Consisting of entering the residence tank 22 for the medium m2.

  The sample S is introduced through the introduction tube 112 through the introduction port 11 with the lid 111 opened in a state where the sample S is placed in a sample cup 131 such as a bowl. The sample holder 13 has a stepped tubular structure that can accommodate the sample cup 131 and hold it in a fixed position.

  The heating furnace 14 is a small electric furnace that receives power from the power source E and generates heat. The power supplied to the heating furnace 14 is controlled by a controller (not shown) according to the heating temperature of the sample S. The periphery of the heating furnace 14 is covered with a high heat resistance heat insulating material 141.

  The housing 12 has an upper and lower two-stage structure, and an air-cooled heat radiator 15 is disposed in the upper stage, and the above-described heat insulating material 141 is accommodated in the lower stage. The upper part is open to the atmosphere, and air is appropriately blown from the fan F1 to the air-cooling radiator 15 to suppress overheating in the vicinity of the introduction pipe 112.

  The air-cooled heat radiator 16 disposed on the lower side of the housing 12 has substantially the same structure as the air-cooled heat radiator 15 described above, and is appropriately cooled by blowing air from the fan F2. As a result, the induction attachment tube 17 is cooled via the shield tube 18.

  The shield tube 18 is provided so as to penetrate the air-cooled heat radiator 16, the upper end portion thereof is joined to the outer peripheral side of the downstream end portion 13 a of the sample holder 13, and the lower end portion thereof is the upstream port 192 of the three-way valve 19. It is joined to.

  The induction attachment tube 17 is inserted in the shield tube 18 and is longer than the shield tube 18. The upper opening portion 17 a of the induction attachment tube 17 is not fixed to the downstream end portion 13 a of the sample holder 13, is detachable, and can move within the shield tube 18.

  The three-way valve 19 includes a body 194 having a supply port 191, an upstream port 192, and a downstream port 193, a valve 195 having a T-shaped three-port housed therein, and a lever 196 that rotates the valve 195. Become.

  The solvent tank 21 stores (organic) solvent m1 such as tetrahydrofuran (THF) or ethanol. The solvent m1 in the solvent tank 21 is pumped to the supply port 191 of the three-way valve 19 by a pump or a syringe (not shown) (solvent supply means).

  If necessary, the retention tank 22 also stores the same or different solvent m2 as the solvent m1 in the solvent tank 21, and the lower opening 17b of the induction attachment tube 17 is immersed in this solvent. . The retention tank 22 includes an exhaust port 221 with a check valve that discharges the carrier gas G1 discharged from the lower opening 17b of the induction attachment pipe 17 to the outside. The carrier gas G1 is introduced from a gas port 113 provided on the upstream side of the introduction pipe 112.

  Incidentally, as shown in FIG. 2, the seal gas G <b> 2 is introduced into the downstream end 13 a of the sample holder 13 from the gas port 133. With this seal gas G2, the gap between the downstream end portion 13a of the sample holder 13 and the upper opening 17a of the guide attachment tube 17 and the gap between the guide attachment tube 17 and the shield tube 18 are gas-sealed. For the carrier gas G1 and the seal gas G2, helium gas or nitrogen gas is used.

  The carrier gas G1 including the introduction pipe 112, the sample cup 131, the sample holder 13, the induction attachment pipe 17, the shield pipe 18, the three-way valve 19 and the like, and the passage for the volatile decomposition component of the sample S are all made of stainless steel. This prevents components other than volatile decomposition components from being collected and collected.

<Action>
(1) First collection and recovery step (collection and recovery of volatile components)
First, the lever 196 of the three-way valve 19 is switched to bring the valve 195 into the state (first position) shown in FIG. 3 (the casing 12 and the like are omitted and the main part is shown). Then, the intermediate portion (extending portion) of the guide attachment tube 17 is inserted into the through-passage of the valve 195, and the upper opening portion 17a of the guide attachment tube 17 is attached to the downstream end portion 13a of the sample holder 13 (first arrangement). .

  A sample cup 131 containing a sample S such as a polymer material is inserted from the insertion port 11 and held in the sample holder 13. Then, after flowing the carrier gas G1 and the seal gas G2 to purge each passage and gap, the heating furnace 14 is operated while flowing the carrier gas G1 and the seal gas G2, and the sample S in the sample holder 13 is brought to a desired temperature. Heat. The lower opening 17b of the induction attachment tube 17 is immersed in the solvent m2 of the residence tank 22 after the heating of the sample is started.

  In this way, volatile components (components such as low molecular weight, low boiling point, and low polarity) V1 in the volatile decomposition components generated from the sample S are discharged from the lower opening 17b of the induction attachment tube 17. A volatile component is collected and collected in the residence tank 22 by dissolving in the solvent m2. In the case where the volatile component is not analyzed, the solvent m2 may not be provided, or it may be changed to a suitable solvent for GC analysis or the like, or it may be changed to a solid adsorbent. .

(2) Second collection / recovery step (collection / recovery of non-volatile components)
Next, in the shield tube 18, the upper opening portion 17 a of the induction attachment tube 17 is separated from the downstream end portion 13 a of the sample holder 13 and lowered to the downstream port 193 of the three-way valve 19. Then, the lever 196 of the three-way valve 19 is switched to bring the valve 195 into the state shown in FIG. 4 (second position). As a result, the supply port 191 and the upper opening 17a of the guide attachment tube 17 are in communication (second arrangement). In this state, when the solvent m1 is caused to flow from the solvent tank 21 to the supply port 191 of the three-way valve 19, the solvent m1 is introduced into the induction attachment tube 17. Thereby, among the volatile decomposition components generated in the first collection and recovery step described above, unrecovered hardly volatile components (high molecular weight, high boiling point) that are cooled by the air-cooling radiator 16 and adhered to the inner wall of the induction attachment tube 17 or the like. , Components such as high polarity) V2 is dissolved in the solvent m1. When this solvent m1 (or solution) flows into the solvent m2 in the retention tank 22 from the lower opening 17b of the induction attachment tube 17, the hardly volatile component V2 is transferred to the solvent m2 in the retention tank 22 in the same manner as the volatile component V1. It will be collected. In addition, the collection efficiency of the hardly volatile component V2 can be improved by repeatedly introducing the solvent m1 into the induction attachment tube 17 as appropriate. Further, for the purpose of reducing the amount of solvent, etc., after the solvent m2 in which the volatile component is dissolved is caused to flow back to the solvent tank 21 through the induction attachment tube 17, the above-described operation can be repeated.

(3) Analysis By analyzing the solvent m2 of the retention tank 22 obtained in this manner with the high performance liquid chromatograph 3, various products generated by heating the sample S can be analyzed almost without leakage. Useful structural information can be obtained comprehensively.

《Analysis example》
An example analyzed using the chromatograph 1 of a present Example is shown. Sample S made of polybutylene terephthalate (PBT) was heated to 500 ° C. in heating furnace 14. At this time, a carrier gas G1 and a seal gas G2 made of nitrogen were flowed at a rate of 70 mL / min and 10 mL / min, respectively. In addition, the downstream part of the induction attachment tube 17 was filled with quartz wool to increase the area where the decomposition product of the sample S contacts in the induction attachment tube 17.

  Thus, the first collection and recovery step and the second collection and recovery step described above were performed, and the analysis by the high performance liquid chromatograph 3 was performed. As a result, components that could not be detected by conventional gas chromatographs could be detected. Moreover, all of the PBT decomposition products confirmed by MALDI-MS (Matrix Assisted Laser Desorption / Ionization-Mass Spectrometry) analysis could also be detected by the chromatograph 1 of this example. Thus, it was confirmed that the volatile decomposition component of the sample S can be analyzed almost without leakage by using the chromatograph 1 of the present example.

13 Sample holder 14 Heating furnace (heating means)
16 Air-cooled radiator (cooling means)
17 Induction attachment pipe 18 Shield pipe 19 Three-way valve (switching valve)

Claims (8)

A sample holder that holds a sample in a gas flow path into which a carrier gas flows, and has a volatile decomposition component generated from the sample and a downstream end from which the carrier gas flows out;
Heating means for heating the sample held in the sample holder;
A detachable upper opening at the downstream end of the sample holder, an extending part extending from the upper opening, and a lower opening on the downstream side of the extending part, guide the volatile decomposition component. Or an induction attachment tube attached to the inner wall;
And a switching valve capable of switching between a first position and a second position,
Can Ru is clamped by the upper opening of the induction attachment pipe extending portion of the induction attachment pipe by interpolation to the switching valve when said first position to the downstream end portion of said sample holder,
Supplying a solvent over the opening of the induction attachment tube is detached from the downstream end portion of said sample holder dissolving at least a portion of volatiles decomposition component adhering to the inner wall of the induction attachment tube when said second position An apparatus for collecting and collecting volatile decomposition components, wherein the upper opening of the guide attachment tube can be communicated with a supply port.   2. The volatile decomposition component collection according to claim 1, further comprising a shield tube interposed between the downstream end portion of the sample holder and the upstream end portion of the switching valve and configured to insert and shield the induction attachment tube. Recovery device. Furthermore, the volatile decomposition component collecting collecting apparatus according to claim 1 or 2 that obtained was clamped by while being a gas seal the upper opening of the guide attachment tube and the downstream end of the specimen holder.   Furthermore, the volatile decomposition | disassembly component collection collection apparatus in any one of Claims 1-3 provided with the cooling means which cools at least one part of the said induction | attachment attachment pipe | tube.   Furthermore, the volatile decomposition | disassembly component collection collection apparatus in any one of Claims 1-4 provided with the solvent supply means which supplies the said solvent to the supply port of the said switching valve.   Furthermore, the volatile decomposition | disassembly component collection collection apparatus in any one of Claims 1-5 which have a retention tank in which the said solvent is retained while the lower opening part of the said induction | attachment attachment pipe | tube is immersed.   A liquid chromatograph comprising the volatile decomposition component collection and recovery device according to claim 1. The volatile component derived from the lower opening of the induction attachment tube is analyzed by a gas chromatograph with the switching valve of the volatile decomposition component collection and recovery device according to any one of claims 1 to 6 in the first position. Gas analysis process;
A liquid analysis step of analyzing, by a liquid chromatograph, a hardly volatile component dissolved in the solvent derived from the lower opening of the induction attachment tube with the switching valve set to the second position after the gas analysis step;
A volatile decomposition component analysis method comprising: