JP3109378U - Polymeric substance analysis equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gel permeation chromatograph (GPC) apparatus that can efficiently supply samples to a sample loop in a short time and can be automated when analyzing a plurality of samples continuously. obtain.
SOLUTION: A sample loop 16; a sample selection unit 11b that enables a predetermined amount of sample to be collected by selecting a predetermined sample container 12a from a plurality of sample containers 12a; and a sample selection unit 11b that is selected by the sample selection unit 11b. A weighing unit 14 for weighing and collecting a predetermined amount of sample from the sample container 12a, a conduit for supplying the sample collected by the weighing unit 14 to the sample loop 16, and the sample from the sample loop to the GPC column 15 The autosampler 11 provided with a switching valve 11a for switching the pipe line to any one of the pipe line for supplying the liquid and the pipe line through which the sample circulates and the pipe line through which the cleaning solvent flows through the GPC column 15 is provided.
[Selection] Figure 2

Description

  The present invention relates to a polymer material analyzing apparatus for analyzing a molecular weight distribution of a polymer material itself or a product manufactured using the polymer material, and more particularly to a gel permeation chromatograph (GPC) apparatus.

In managing the quality of the polymer materials themselves and the products manufactured using the polymer materials (hereinafter collectively referred to as “polymer substances”), the molecular weight distribution of the molecules constituting them It is extremely important to know.
Here, the molecular weight distribution is generally measured using a gel permeation chromatograph (hereinafter referred to as GPC) apparatus (see, for example, Patent Document 1 and Non-Patent Document 2). Recently, a GPC-FTIR apparatus in which a Fourier transform infrared spectrometer (FTIR) is connected as a detector to this GPC apparatus has been used extensively, and components are continuously added due to differences in molecular weight using a GPC column. Each component separated using FTIR is irradiated with infrared light to determine the molecular structure from the absorption waveform.
Japanese Patent Laid-Open No. 4-54452 (see detailed description of the invention) Materials for the 6th Polymer Analysis Discussion Meeting (held on November 5-6, 2001, edited by the Analytical Society of Japan)

FIG. 5 is a schematic diagram illustrating a configuration of a conventional GPC-FTIR apparatus.
The GPC-FTIR apparatus includes a column oven 100 that holds the GPC column 105 at a predetermined temperature, a sample container 120a that contains a sample, and a sample oven 120 that holds the sample at a predetermined temperature. A carrier container 109 that contains a carrier as a mobile phase solvent to be carried out, a pump 107 that feeds the carrier from the carrier container 109, and a syringe 101 for collecting a predetermined amount of sample from the sample container 120a.

  The column oven 100 is provided with a plurality of sample loops 106, 106,... That hold a certain amount of sample collected from the sample container 120a by the syringe 101, and a GPC column 105 that separates the samples. . Further, the column oven 100 is provided with two valves, that is, a 6-port valve 103 and a 3-port valve 102, so that the flow of the sample and the carrier can be switched.

One of the three ports of the three-port valve 102 is connected to the pipe line (i) of the sample container 120a, and the other one is connected to the pipe line (ii) of the carrier container 109. Another port located between these two ports has a conduit
(iii) is connected.
In addition to this pipe line (iii), the 6-port valve 103 includes a pipe line (iv) of the syringe 101, pipe lines (v) and pipes (vi) at both ends of the sample loop 106, and a pipe line of the GPC column 105 ( viii) and the conduit (vii) of the carrier container 109, respectively.
Switching valves 104a and 104b for selecting a predetermined sample loop 106 are attached to one end of the pipe line (v) and the pipe line (vi).

In the column oven 100 configured as described above, a predetermined amount of sample is collected from the sample container 120a by the syringe 101 in the following procedure, sent to the predetermined sample loop 106, and further supplied from the sample loop 106 to the GPC column 105.
First, one sample container 120a is set inside the sample oven 120, the pipe line (i) of the sample container 120a is connected to one port of the three-port valve 102, and the pipe line (i) and the pipe line (iii The three-port valve 102 is switched so as to communicate with each other.

Further, a syringe 101 for collecting a predetermined amount of sample from the sample container 120a is connected to the pipe line (vi), and the 6-port valve 103 is switched so that the pipe line (iii) and the pipe line (iv) communicate with each other. . In this state, the syringe 101 is operated to collect a predetermined amount of sample from the sample container 120a.
When this operation is completed, the 6-port valve 103 is switched so that the pipe line (iv) and the pipe line (v) communicate with each other, and the switching valve 104a is operated to select a predetermined sample loop 106. Then, the syringe 101 is operated to send a predetermined amount of sample to the predetermined sample loop 106.
Thus, the supply of the sample to one sample loop 106 is completed.

In order to supply different types of samples to another sample loop 106, prior to switching, each line through which a sample flows when a predetermined amount of sample is supplied to the sample loop 106 (lines (iii), (iv), (v)) is washed with a carrier. For this purpose, the three-port valve 102 is switched so that the pipe line (i) and the pipe line (iii) communicate with each other, and the pipe line (iii) and the pipe line (vi) and the pipe line (v) and the pipe line are switched. The 6-port valve 103 is switched so that the passage (iv) is in communication.
Next, the container 120a is replaced with a waste liquid container. In this state, by filling the syringe 101 with the carrier solvent and performing an extrusion operation, the carrier in the syringe 101 is sent to the pipes (iv), (v), (vi), (iii), (i). The pipe and sample loop 106 are cleaned.
Further, by driving the pump 107, the carrier in the carrier container 109 flows through the pipe lines (vii) and (viii) and the GPC column 105, and these are washed.
After the cleaning is completed, the waste liquid container is replaced with the next sample container 120a.

  When cleaning is completed by the above procedure, the sample container 120a to be supplied to the sample loop 106 is replaced next, and a predetermined amount of sample is sent to the predetermined sample loop 106 in the same procedure as described above. By repeating this procedure, different types of samples can be supplied to each of the eight sample loops 106.

In order to supply the sample held in the predetermined sample loop 106 to the GPC column 105, the pipe line (vii) and the pipe line (vi), and the pipe line (v) and the pipe line (viii) are connected to each other. The 6-port valve 103 is switched, and the switching valves 104b and 104a are operated to select a predetermined sample loop 106. Then, the pump 107 is driven to send out the carrier from the carrier container 109.
As a result, the carrier is sent to the predetermined sample loop 106, and the sample of the sample loop 106 is supplied to the GPC column 105.

In order to sequentially analyze the samples held in the eight sample loops 106, it is necessary to clean the pipes (vi), (v), (viii) and the GPC column 105 prior to sample switching. Therefore, when the sample to be sent to the GPC column 105 is switched, the pump 107 is driven again, and a carrier several times the capacity of the GPC column 105 is transferred from the pipes (vi), (v), (viii) to the GPC column. These are then washed. Thereafter, the switching valves 104 a and 104 b are operated to select the next sample loop 106, the pump 107 is driven, and the sample of the sample loop 106 is sent to the GPC column 105.
By repeating the above operation, the eight samples held in the eight sample loops 106 can be sequentially sent to the GPC column 105 for component separation and analysis.

  However, in the column oven 100 having the above configuration, the sample container 120a is replaced, the sample is collected by the syringe 101, the pipes (i) to (viii) and the GPC column 105 are washed, and the sample container 120a is replaced. The operation has to be repeated as many times as the number of samples, and there is a problem that the work is complicated and it takes a lot of time for sampling and analysis. In addition, these operations rely on manual operations, but depending on the type of carrier, there is a problem that the pungent odor is strong, the operation must be performed in a poor environment, and the burden on the operator is heavy. In addition, since sample switching is performed manually, for example, there is a risk of errors due to human error or measurement errors due to forgetting or insufficient cleaning when switching samples. It was.

  In addition, when the above operation is automatically performed, it is advantageous in terms of cost to use a commercially available personal computer (PC). However, due to changes in the specifications of the OS and application software by the PC manufacturer and application software manufacturer, There is a problem that it is troublesome to deal with version upgrades of application software and OS each time. Furthermore, if application software and OS that have been used for many years are abolished due to the manufacturer's convenience, introduction of alternative PC, application software, and OS must be considered, and alternative PC, application software, and OS are expected. There is an inconvenience that it takes a long time to get a guarantee of whether or not to operate normally. In addition, there is a problem that it is difficult for application software manufacturers and OSs to change specifications freely by users.

  The present invention was made in view of the above problems, and when performing analysis of a plurality of samples continuously, it is possible to efficiently supply a sample to an injector such as a sample loop in a short time, In addition, it is possible to obtain a gel permeation chromatograph (GPC) device that can be automated, and to freely change the program on the user side without using a specific PC incorporating a specific OS or dedicated application software. It is an object of the present invention to obtain a GPC device provided with a control unit capable of performing the above.

  In order to solve the former problem, the device according to claim 1 is an analysis of a macromolecular substance that collects a predetermined amount of sample from a sample container into an injector and supplies the sample to a GPC column in a column oven. In the apparatus, a predetermined sample container is selected from among a plurality of sample container sets that can set a plurality of sample containers containing the same or different types of samples, at least one injector, and a plurality of sample containers. A sample selection unit that enables sample collection, a weighing unit that measures and collects a predetermined amount of sample from the sample container selected by the sample selection unit, and the injector that collects the sample collected by the measurement unit A pipe to supply to the GPC column from the injector Control of the operation of the autosampler including a sample supply line and a switching valve for switching to one of the cleaning lines, and the operation part of the autosampler including the sample selection unit, the metering unit, and the switching valve And a control unit that performs the above.

According to this configuration, a plurality of sample containers containing the same or different types of samples are set in a sample container holding unit such as a sample oven. The sample container is selected by the control unit switching the sample selection unit. When the analysis of one sample is completed, the control unit determines the sample to be analyzed next and switches the sample selection unit, so there is no need to reset the sample container.
In addition, since the measurement unit automatically performs measurement of the sample sent from the sample container to the injector, it is not necessary to perform measurement using a syringe.
In addition, the cleaning operation prior to sample switching can be performed easily and in a short time by switching the switching valve based on a command from the control unit and driving the pump to circulate the cleaning solvent such as the carrier. It can be finished with.

In order to solve the latter problem, the invention described in claim 2 is configured such that the control unit performs operation control of each operation unit of the autosampler by sequence control.
The continuous analysis of a plurality of samples by the GPC apparatus having the above configuration is performed by selecting a sample by the sample selection unit, weighing the sample by the weighing unit, supplying the sample to the GPC column, washing the pipeline through which the sample flows, and by the sample selection unit. This is done by a series of operations such as selection of the next sample. Therefore, such a series of operations can be controlled by sequence control. Therefore, it is possible to obtain a control unit that allows the user to freely rearrange programs without using a specific PC incorporating a specific OS or dedicated application software.
The temperature control of the GPC column oven and the control of the flow rate and the pressure when the sample is supplied to the GPC column may be performed by other control such as feedback control in addition to the sequence control described above.

The injector may be provided with a common (single) injector for a plurality of sample containers, or may be provided with a plurality corresponding to each of the plurality of sample containers as described in claim 3. Good.
In this way, after a predetermined amount of sample is sent from each sample container to each of the injectors and held, each sample can be sequentially sent from a plurality of injectors to the GPC column for separation and analysis. When analyzing a large number of samples, the analysis time can be greatly shortened. Moreover, about the same kind of sample, mixing of a different sample can be suppressed by using a specific injector.

According to the analyzer of the present invention, the component separated by the GPC column is converted into a Fourier transform infrared spectrometer, a liquid chromatography tester, an infrared analyzer, a differential refractometer (RI). Or it can send to other analyzers, such as a mass spectrometer, so that it may analyze.
In addition, as an injector which sends a sample to a GPC column, the thing of a various form can be used, For example, as described in Claim 5, a loop thing can also be used.

  According to the present invention, sample selection includes sample supply from multiple sample containers to the sample loop, sample supply from the sample loop to the GPC column, washing of the pipeline through which the sample flows, and switching to a different type of sample. It is possible only by the switching operation of the section and the switching valve, and the analysis time of a plurality of types of samples can be greatly shortened, and the work load on the operator can be reduced.

In addition, by simply setting multiple sample containers in the sample oven, it is possible to automatically perform quantitative sample collection, supply to the sample loop, supply to the GPC column, washing, and selection of the sample to be used for the next analysis. become.
Furthermore, by adopting sequence control as a control unit for controlling the operation of each operation unit of the autosampler, it is not necessary to use a specific PC, and the user can freely rearrange programs.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a block diagram illustrating a configuration of a GPC device according to an embodiment of the present invention.
As shown in FIG. 1, the GPC apparatus according to this embodiment constitutes a GPC-FTIR apparatus that sends components separated by a GPC column 15 to a Fourier transform infrared spectrometer (FTIR) to perform spectral analysis. is there.

  The GPC apparatus can set a column oven 10 that keeps the temperature of the GPC column 15 at a predetermined temperature and a plurality of (eight in the illustrated example) sample containers 12a at a time, and a sample stored in the sample container 12a is determined in advance. A sample oven 12 that holds the temperature, an autosampler 11 that is provided in the column oven 10 and weighs and takes out a predetermined amount of sample from a predetermined sample container 12a, and a predetermined amount of sample taken out by the autosampler 11 In addition to the operation control of each operation unit included in the autosampler 11, the pump 17 for controlling the pump 17, as well as the pump 17 for transporting to the GPC column 15, the carrier container 19 for accommodating the carrier connected to the pump 17. , Column oven 10, autosampler 11 and sample And a control unit 30 for controlling the temperature or the like of Bun 12.

As the autosampler 11, for example, a commercially available one can be used as disclosed in, for example, Japanese Patent Laid-Open Nos. Hei 8-220070 and 2004-271241. The autosampler 11 may be provided inside the column oven 10 as illustrated, or may be provided separately from the column oven 10.
2 and 3 are diagrams for explaining the configuration of the autosampler used in this embodiment, and FIG. FIG. 3 shows a so-called INJECT state in which a sample is sent from the sample loop 16 to the GPC column 15 by the carrier.

  As shown in the figure, the autosampler 11 is connected to each of the sample containers 12a by a pipe line, and a sample selection valve 11b that selects the predetermined sample container 12a so as to send the sample of the predetermined sample container to the sample loop 16. And a 6-port valve 11a for switching between the loaded state and the injecting state, a sample loop 16 connected to the 6-port valve 11a, and a metering for metering out the sample from the sample container 12a And a pump 14.

The sample selection valve 11b incorporates a channel for switching each of the sample containers 12a and nine pipes connected to the drain, and the channel is set to a predetermined sample according to a command signal from the control unit 30 (see FIG. 1). Switch to a conduit connected to the container 12a or a drain conduit.
As shown in FIG. 2, in this embodiment, the pipe line that connects the sample selection valve 11b and the 6-port valve 11a in a communicating manner is one of the six ports included in the 6-port valve 11a (hereinafter referred to as the “port”). This port is designated as “No. 6” port and is connected to “No. 1”, “No. 2”... “No. 5” port in the clockwise direction).

  The sample loop 16 can hold, for example, 750 μl of sample, and may share a single sample loop 16 for eight types of samples, or as in the conventional example of FIG. The switching valves (reference numerals 104a and 104b in FIG. 5) of the sample loop 16 may be provided, and eight loops 16 corresponding to each of the eight types may be provided. In this embodiment, the pipe lines at both ends of the sample loop 16 are connected to the first port and the fourth port of the 6-port valve 11a.

  The metering pump 14 is provided outside the column oven 10, and is connected to the fifth port of the 6-port valve 11a via the switching valve 14a. A buffer 14b having a volume of, for example, about 2 ml may be provided in the middle of the pipe line connecting the switching valve 14a and the fifth port. A carrier container 13 that accommodates a carrier is connected to the switching valve 14a, and is connected to the fifth port of the 6-port valve 11a via the conduit.

A pipe line of a pump 17 for sending a carrier for sample conveyance to the sample loop 16 is connected to the second port of the 6-port valve 11a, and the GPC column 15 is connected to the third port.
Next, the operation of the autosampler 11 having the above configuration will be described with reference to the flowchart of FIG.
The control unit 30 sequentially executes a series of procedures as shown in FIG. 4 by sequence control.
When analyzing the sample in the autosampler 11 having the above-described configuration, the sample selection valve 11b selects the sample container 12a containing the sample to be analyzed this time according to a command from the control unit 30 (step S1). Further, the 6-port valve 11a is switched to the load state according to a command from the control unit 30 (step S2). Further, the switching valve 14a is switched so that the metering pump 14 and the fifth port communicate with each other (step S3).

In this state, the metering pump 14 is driven by a command from the control unit 30, and a predetermined amount of sample is taken out from the sample container 12a. The sample taken out flows from the 6th port of the 6 port valve 11a to the 1st port through the sample selection valve 11b, and is sent to the sample loop 16 (step S4).
Thereafter, the 6-port valve 11a is switched to the INJECT state shown in FIG. 3 according to a command from the control unit 30 (step S5). Then, by driving the pump 17, the carrier of the carrier container 19 is sent from the 2nd port to the sample loop 16 via the 1st port, and the sample held in the sample loop 16 is transferred to the 4th and 3rd ports together with the carrier. It is sent to the GPC column 15 through the port (step S5).
Thus, the analysis operation for one type of sample is completed.

  Note that the temperature control of the column oven 10, the temperature control of the sample oven 12, and the flow rate and pressure of the sample supplied to the GPC column 15 are switched on based on the detection results of a temperature sensor, a flow meter, a pressure sensor, etc. Although it is possible to perform control by sequence control by setting it to be turned off, it is possible to more accurately perform management by partially using other control such as feedback control.

The cleaning operation for performing the analysis operation of the next sample is performed according to the following procedure.
In response to a command from the control unit 30, the channel of the sample selection valve 11b is switched so as to select a drain line (step S7). Further, the pump 17 is driven in the INJECT state of FIG. 3 (step S8). Further, the switching valve 14a is switched so that the carrier of the carrier container 13 is sent to the 6-port valve 11a by the metering pump 14 (step S9). In this state, the metering pump 14 is driven (step S10).

As a result, the carrier in the carrier container 19 flows from the 2nd port and 1st port of the 6-port valve 11a to the sample loop 16, and is further sent from the 4th port and 3rd port to the GPC column 15 on this path. A certain line, sample 16 and GPC column 15 are cleaned. On the other hand, the carrier in the carrier container 13 is sent from the 5th port and 6th port to the sample selection valve 11b and discharged from the drain conduit. Then, the pipe existing in this process is washed.
When the cleaning is completed, the sample container 12a to be analyzed next is selected by the sample selection valve 11b (step S1), the 6-port valve 11a is switched to the loading state of FIG. 2 (step S2), and the sample is selected. The loop 16 is supplied with the next sample to be analyzed.
By repeating the above procedure, the analysis operation of eight types of samples can be performed sequentially.

  In the above embodiment, the set time of eight types of samples is shortened from about 60 minutes to about 10 minutes, and errors and measurement errors due to human error of the operator can be almost eliminated. In addition, since all the above operations are automatically performed by sequence control, the work time of the worker in a bad environment such as bad odor is greatly reduced, and the work load of the worker is reduced.

Although preferred embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments.
For example, in the above description, a single sample loop 16 is used, and eight samples are sequentially sent to the GPC column 15 by washing and switching of the sample selection valve 11b and the 6-port valve 11a. Similarly to the example, eight sample loops 16 may be provided in the autosampler 11 in advance, and the eight sample loops 16 may be sequentially sent to the GPC column 15.
Moreover, in said embodiment, although the two containers shown by the code | symbol 13 and the code | symbol 19 are shown and demonstrated as a carrier container, these may be common.

  The GPC apparatus of the present invention is not limited to a Fourier transform infrared spectrometer (FTIR), but may be connected to other analyzers such as liquid chromatography, infrared analyzer, differential refractometer (RI), or mass spectrometer. Is possible.

It is a block diagram explaining composition of a GPC device concerning one embodiment of the present invention. It is a figure explaining the structure of the autosampler used in this embodiment, and shows the state of a load that measures and supplies the sample in the sample container to the sample loop that contains the sample. It is a figure explaining the structure of the autosampler used in this embodiment, and shows the state of injection for sending a sample from the sample loop to the GPC column by the carrier. It is a flowchart explaining the control procedure by the control part of this embodiment. It is the schematic concerning the prior art example of a GPC-FTIR apparatus and explaining the structure.

Explanation of symbols

10: Column oven 11: Autosampler 11a: 6-port valve (switching valve)
11b: Sample selection valve (sample selection unit)
12: Sample oven (sample container set part)
12a: Sample container 13: Carrier container 14: Metering pump (metering unit)
15: Column 16: Sample loop (injector)
17: Pump 19: Carrier container 30: Control unit

Claims (5)

In a polymer substance analyzer that collects a predetermined amount of sample from a sample container into an injector and supplies the sample to a GPC column in a column oven,
A sample container setting unit capable of setting a plurality of sample containers containing the same or different types of samples;
At least one injector, a sample selection unit for selecting a predetermined sample container from the plurality of sample containers and enabling collection of a predetermined amount of sample, and the sample container selected by the sample selection unit A weighing unit for weighing and collecting a predetermined amount of sample from the pipe, a pipe for supplying the sample collected by the weighing section to the injector, a pipe for feeding the sample from the injector to the GPC column, and washing. An autosampler comprising a switching valve for switching to one of the pipelines to be performed;
A control unit for controlling the operation of the operation unit of the autosampler including the sample selection unit, the metering unit, and the switching valve;
A polymer substance analyzing apparatus characterized by comprising:   2. The polymer substance analyzing apparatus according to claim 1, wherein the control unit performs operation control of each operation unit of the autosampler by sequence control.   The polymer substance analyzing apparatus according to claim 1, wherein a plurality of the injectors are provided corresponding to each of the sample containers.   The component separated by the GPC column is sent to another analyzer such as a Fourier transform infrared spectrometer, a liquid chromatography tester, an infrared analyzer, a differential refractometer or a mass analyzer for analysis. The polymer substance analyzer according to any one of claims 1 to 3.   5. The polymer substance analyzing apparatus according to claim 1, wherein the injector is of a loop shape.

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