JP2008241274A - Device and method for measuring molecular weight distribution of organic high polymer component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device and method, capable of accurately measuring the molecular weight distribution of an organic high polymer component such as glue or gelatine included in an electrolyte. <P>SOLUTION: The device includes a solid phase cartridge 5 as an organic high polymer component collecting part for collecting the organic high polymer component from a sample solution, a sample loop 20 as a weighing recovery part for weighing and recovering an elution liquid of the organic high polymer component separated by elution from this organic high polymer component collecting part, a size removing column 21 as an organic high polymer component separating part for sequentially separating the elution liquid of the organic high polymer component of the specific volume recovered by this weighing recovery part in response to molecular weight, and a detector 22 as a detecting part for providing the molecular weight distribution of the organic high polymer component based on its characteristic detecting value by sequentially detecting the predetermined characteristic of the elution liquid of the organic high polymer component sequentially separated from this organic high polymer component separating part in response to the molecular weight. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to an organic polymer component molecular weight distribution measuring apparatus and a measuring method thereof, and more particularly to an apparatus for measuring a molecular weight distribution of organic polymer components such as glue or gelatin contained in an electrolyte for metal refining or plating. .

  To the metal smelting and plating electrolytes, glue and gelatin are added in order to control crystal growth and improve the mechanical strength and appearance of the product. Such glue and gelatin in the electrolytic solution are gradually decomposed by the influence of free acid, heat and electrolysis, and the molecular weight is lowered. There is a relationship between the molecular weight of glue and gelatin and the effect on the electrodeposition state, and the effect is lost as the degradation of glue and gelatin proceeds. Therefore, in order to keep the effects of glue and gelatin constant, it is necessary to determine the appropriate addition conditions by measuring the molecular weight distribution of glue and gelatin in the electrolyte.

  Size exclusion chromatography is known as a representative method for measuring the molecular weight distribution of glue and gelatin. When measuring the molecular weight distribution of glue or gelatin in an electrolyte sample by such size exclusion chromatography, the electrolyte solution contains a high concentration of inorganic salts. There are problems such as large interference and deterioration of the column. Therefore, it is necessary to effectively remove inorganic salts before introducing the electrolyte solution sample into the chromatograph apparatus. Further, since the concentration of glue or gelatin is as low as about 1/1000 of the main component of the electrolyte sample, it is desirable to concentrate glue or gelatin in order to accurately measure the molecular weight distribution of glue or gelatin. .

  As a molecular weight distribution measuring apparatus using such size exclusion chromatography, a method for measuring the concentration and molecular weight distribution of glue and gelatin contained in an electrolyte by high performance liquid chromatography combined with a column switching method has been proposed. (For example, refer to Patent Document 1). In addition, a method of performing a series of operations based on the flow analysis method by adsorbing organic polymer components such as protein, glue and gelatin contained in the sample to the resin, separating them from the sample, and introducing them to gel diffusion chromatography for analysis. Has also been proposed (see, for example, Patent Document 2).

JP 2001-337081 A (paragraph number 0010) JP 2002-296260 A (paragraph number 0008)

  However, in the methods of Patent Documents 1 and 2, the molecular weight distribution of glue or gelatin is measured by quantifying the glue or gelatin with molecular weight fractionation, but there is a problem that the quantitative value is not accurate. This is because the detection sensitivity of glue and gelatin is not necessarily constant between the molecular weights, but the influence is not reflected in the quantitative calculation. Moreover, in the method of patent document 1, since the sample solution in an analysis process is diluted with a mobile phase, there exists a problem that the S / N ratio at the time of a detection falls.

  Therefore, in view of such a conventional problem, the present invention can accurately measure the molecular weight distribution of an organic polymer component such as glue or gelatin contained in an electrolyte solution, etc. An object is to provide a measuring apparatus and a measuring method thereof.

  In order to solve the above-described problems, an organic polymer component molecular weight distribution measuring apparatus according to the present invention includes an organic polymer component collecting unit that collects an organic polymer component from a sample solution, and an organic polymer component collecting unit. Weighing and collecting the organic polymer component eluate separated by elution and measuring and collecting the organic polymer component eluate of a certain volume collected by this weighing and collecting unit in order according to the molecular weight The polymer component separation unit and the organic polymer component eluate sequentially separated from the organic polymer component separation unit according to the molecular weight are sequentially detected for predetermined characteristics, and based on the detected value of the characteristics, And a detector for obtaining a molecular weight distribution of molecular components. In this organic polymer component molecular weight distribution measuring apparatus, the organic polymer component separation unit is preferably a size exclusion column, and the metering recovery unit is preferably a constant volume flow path such as a sample loop. The organic polymer component collecting part preferably has a solid phase extraction agent that collects the organic polymer component from the sample solution and separates the organic polymer component by elution, and the solid phase extraction agent has 18 carbon atoms. More preferably, it is a solid phase extractant having the following alkyl group and a pore diameter of 50 nm.

  The method for measuring the molecular weight distribution of an organic polymer component according to the present invention includes a step of collecting an organic polymer component from a sample solution, a step of separating the collected organic polymer component as an eluate, and this separation. A step of measuring and recovering the eluate of the collected organic polymer component, a step of sequentially separating the collected eluate of a certain volume of the organic polymer component according to the molecular weight, and a separation according to the molecular weight. And a step of sequentially detecting predetermined characteristics of the eluate of the organic polymer component and obtaining a molecular weight distribution of the organic polymer component based on a detection value of the characteristic. In this molecular weight distribution measurement method for organic polymer components, a plurality of standard samples having different molecular weights of organic polymer components are prepared, and a solution in which the concentrations of these standard samples are changed stepwise is used as a standard solution. Create a calibration curve showing the relationship between the concentration of each standard sample and the detected value for each molecular weight of the polymer component, and obtain the molecular weight distribution from the relationship between the concentration of the organic polymer component and the molecular weight based on these calibration curves. It is preferable to provide a step of quantifying the polymer component according to molecular weight.

  According to the present invention, there are provided an organic polymer component molecular weight distribution measuring apparatus and a measurement method thereof capable of accurately measuring the molecular weight distribution of an organic polymer component such as glue or gelatin contained in an electrolyte or the like. Can do.

  In particular, by providing a metering recovery unit consisting of a constant volume flow path such as a sample loop, the organic polymer component from the organic polymer component collection unit such as a solid phase cartridge filled with a solid phase extraction agent is obtained. The eluate can be weighed to dilute the eluate and minimize the amount of solvent required to supply the organic polymer component separation section such as a size exclusion column. In addition, the eluent used to elute the organic polymer component from the organic polymer component collector and the mobile phase introduced into the organic polymer component separator together with the organic polymer component must have the same composition. Thus, it is possible to select an eluent and a mobile phase having different compositions.

  In addition, if the molecular weight distribution of an organic polymer component is determined based on a calibration curve indicating the relationship between the detected value and concentration of a predetermined characteristic of the eluate of the organic polymer component, the molecular weight distribution of the organic polymer component can be accurately determined. It can be measured well.

  DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a molecular weight distribution measuring apparatus and method for measuring organic polymer components according to the present invention will be described in detail below with reference to the accompanying drawings.

  The molecular weight distribution measuring apparatus for organic polymer components according to the present embodiment includes a pretreatment unit shown in FIG. 1 for pretreatment of a sample solution containing an organic polymer component such as glue or gelatin, and a pretreatment by this pretreatment unit. The recovery / separation / detection unit shown in FIG. 2 collects, separates and detects organic polymer components such as glue or gelatin from the sample solution.

  In the pretreatment section shown in FIG. 1, the upper part of the solid phase cartridge 5 filled with the solid phase extractant is detachably connected to the pipe 6, and this pipe 6 is connected to the pipe 7 via the pump 4. The pipe 7 is connected and can be inserted into any one of a container 1 containing an organic solvent, a container 2 containing water, and a container 3 containing a sample solution. The solid phase extraction agent to be filled in the solid phase cartridge 5 has an alkyl group having 18 carbon atoms and a pore diameter of 50 nm when used for collecting glue or gelatin as an organic polymer component. It is preferable to use the solid phase extraction agent. Further, the weight of the solid phase extraction agent to be filled in the solid phase cartridge 5 may be determined according to the absolute amount of the organic polymer component to be held in the solid phase extraction agent, and if the weight of the solid phase extraction agent is increased. In addition, the weight of the organic polymer component retained by the solid phase extraction agent also increases. Further, as the pump 4, it is preferable to use a peristaltic pump because the piping can be easily replaced even when a component in the sample solution such as the electrolyte is deposited in the flow path.

  In the recovery / separation / detection unit shown in FIG. 2, the top side of the solid-phase cartridge 5 filled with the solid-phase extraction agent holding the organic polymer component pretreated by the pretreatment unit shown in FIG. The pipe 13 is detachably connected, and the pipe 14 is detachably connected to the lower outlet side of the solid phase cartridge 5. For connection of the pipe 13 to the solid phase cartridge 5, an adapter that is commercially available as a dedicated product for the solid phase cartridge can be used. For connection of the pipe 14 to the solid phase cartridge 5, a female luer is used. An adapter can be used. Further, the pipe 13 is connected to the pump 9 or the pump 11 so as to be switched by the three-way valve 12, and the pump 9 and the pump 11 are respectively a container 8 containing a cleaning liquid and a container containing an eluent. 10 is connected to a pipe inserted into the pipe. On the other hand, the pipe 14 is connected to one port of the six-way valve 15. The hexagonal valve 15 is switched between a position where the ports are connected as shown by a solid line in FIG. 2 and a position where the ports are connected as shown by a broken line. At a position where the ports are connected as indicated by a solid line, the pipe 14 is connected to the drain 16 via the sample loop 20. On the other hand, at the position where the ports are connected as shown by the broken line, the pipe 14 is connected to the drain 16 and the container 17 containing the mobile phase is pump 18, sample injector 19, sample loop 20, size exclusion column 21. It is connected to the detector 22 via.

  A method of measuring the molecular weight distribution of the organic polymer component using the organic polymer component molecular weight distribution measuring apparatus of the present embodiment having such a configuration will be described.

  First, in the pretreatment section shown in FIG. 1, the pipe 6 is connected to the upper part of the solid phase cartridge 5 filled with the solid phase extractant, and the pipe 7 is inserted into the container 1 containing the organic solvent. The solvent is passed through the solid phase cartridge 5. The organic solvent put into the container 1 acts to facilitate the penetration of the sample solution into the solid phase extraction agent, and lower alcohol, acetonitrile, or the like can be used as the organic solvent. Next, the pipe 7 is inserted into the container 2 containing water, and water is passed through the solid phase cartridge 5 by the pump 4 to wash away the organic solvent remaining in the solid phase extractant. Next, the pipe 7 is inserted into the container 3 containing the sample solution, the sample solution is passed through the solid phase cartridge 5 by the pump 4, and the organic polymer component is added to the solid phase extractant filled in the solid phase cartridge 5. Hold. The amount of the sample solution that passes through the solid phase cartridge 5 may be determined by confirming the amount of the sample solution containing an organic polymer component that is not insufficient for detection through preliminary experiments. Since the concentration rate of the organic polymer component can be improved by increasing the amount of the sample solution, a sufficient detection intensity can be obtained even if the concentration of the organic polymer component in the sample solution is low.

  Next, the solid phase cartridge 5 filled with the solid phase extractant holding the organic polymer component in this way is removed from the pipe 6 of the pretreatment section, and the pipe 13 is connected to the inlet side at the top of the solid phase cartridge 5. And the pipe 14 is connected to the lower outlet side of the solid phase cartridge 5.

  Next, the three-way valve 12 is connected to the pump 9 at a position where the ports are connected as shown by a solid line in FIG. 2, and the pipe 13 is connected to the pump 9, and the six-way valve 15 is connected as shown by a solid line in FIG. The cleaning liquid placed in the container 8 is caused to flow into the solid phase cartridge 5 by the pump 9 to wash away the contaminated components, and the cleaning liquid is discharged from the drain 16. The cleaning liquid may be of any composition that does not elute the organic polymer component held in the solid phase extraction agent packed in the solid phase cartridge 5. For example, a buffer solution that does not contain an organic solvent may be used. it can. In addition, when using electrolyte solution as a sample solution, in order to avoid precipitation by hydrolysis of a metal component, it is preferable that the pH of a washing | cleaning liquid is acidic-neutral.

  Next, the three-way valve 12 is switched to a position where the ports are connected as indicated by broken lines in FIG. 2, the pipe 13 is connected to the pump 11, and the eluent contained in the container 10 is transferred to the solid phase cartridge 5 by the pump 11. Flow to elute the organic polymer components. As the eluent, for example, a buffer solution containing 20 to 50% of an organic solvent such as acetonitrile or lower alcohol can be used.

  The eluate from the solid phase cartridge 5 passes through a pipe 14 and a hexagonal valve 15 (ports are connected as shown by a solid line in FIG. 2), and is guided to a sample loop 20. When the eluted organic polymer component has been collected in the sample loop 20, the hexagonal valve 15 is switched to a position where the ports are connected as indicated by broken lines in FIG. 2, and the mobile phase placed in the container 17 is pumped. 18, when flowing through the size exclusion column 21 via the hexagonal valve 15, the organic polymer component recovered in the sample loop 20 is introduced into the size exclusion column 21 together with the mobile phase, and the organic polymer component is separated according to the molecular weight. The The volume of the sample loop 20 may be the same as the volume confirmed by the preliminary experiment after confirming the volume of the eluent necessary for elution of the organic polymer component. The size exclusion column 21 may be any size exclusion column capable of separating the target molecular weight range. For example, a size exclusion column having an exclusion limit molecular weight of 100,000 to 1,000,000 can be used. Moreover, as a mobile phase, the mobile phase for normal protein separation can be used.

  The effluent from the size exclusion column 21 is guided to the detector 22 to continuously detect the organic polymer component. As the detector 22, an optical detector or a detector based on a refractive index can be used. For example, an absorbance measurement device using ultraviolet absorption with a wavelength of 205 to 220 nm can be used.

  The measurement result by the detector 22 is represented in the chromatogram with the retention time of the size exclusion column 21 as the horizontal axis and the detection intensity as the vertical axis. The peak of the organic polymer component represented on the chromatogram is divided at a minute interval in the horizontal axis direction, and the peak area is calculated for each divided region. In size exclusion chromatography, since the horizontal axis of the chromatogram is related to the molecular weight, the peak area for each molecular weight can be determined. Note that the closer the chromatogram division width is, the better the approximation is, and the more accurate molecular weight distribution can be obtained.

  A molecular weight calibration curve used in molecular weight determination in size exclusion chromatography can be generated from the relationship between retention time and molecular weight of a size exclusion column by injecting a standard sample of known molecular weight into the size exclusion column. In the molecular weight distribution measuring apparatus of the organic polymer component of the present embodiment, in the recovery / separation / detection unit shown in FIG. 2, the hexagonal valve 15 is switched to a position where the ports are connected as shown by the solid line in FIG. Thereafter, a standard sample having a known molecular weight is injected from the sample injector 19, and the molecular weight is obtained by interpolating the plotted points of the measurement results of the standard sample with the horizontal axis representing the retention time of the chromatogram and the common logarithm of molecular weight. A calibration curve can be obtained. As this standard sample, a protein standard sample commercially available for size exclusion chromatography can be used as an aqueous solution.

  Next, a method for preparing a calibration curve for organic polymer components by molecular weight and a procedure for quantitative calculation will be described. As a standard sample used to prepare a calibration curve, commercially available organic polymer components such as glue or gelatin having different molecular weights can be used, or prepared from organic polymer components such as glue or gelatin to be analyzed.

  In the case of using a commercially available organic polymer component such as glue or gelatin, several types of samples having different molecular weights that cover the molecular weight range to be measured may be prepared. The narrower the molecular weight distribution of each sample, the more accurately the molecular weight can be corrected.

  In addition, when preparing a standard sample from an organic polymer component itself such as glue or gelatin to be analyzed, it can be adjusted by the following method. First, an organic polymer component such as glue or gelatin is used as an aqueous solution, and an acid such as hydrochloric acid is added to this aqueous solution to promote decomposition by heating. By changing the acid concentration and heating temperature, organic polymer components such as glue or gelatin having various molecular weights can be produced. Subsequently, the organic polymer component such as glue or gelatin is molecular weight fractionated by several kinds of ultrafiltration membranes having different fractional molecular weights. First, it is filtered through an ultrafiltration membrane having a large fractional molecular weight, and the obtained filtrate is successively filtered through an ultrafiltration membrane having a small fractional molecular weight. After performing such filtration, it is washed with water 2-3 times on the filtration membrane to remove the added acid. After washing with water, the solvent is evaporated from the concentrated solution remaining on the filter membrane to obtain organic polymer components such as solid glue or gelatin. If the solvent is heated strongly when the solvent is evaporated, the organic polymer component such as glue or gelatin is decomposed. Therefore, the solvent is preferably removed by lyophilization.

  In order to measure the molecular weight of the standard sample thus prepared, the hexagonal valve 15 is switched to a position where the ports are connected as indicated by a solid line in FIG. It is injected into the size exclusion column 21, and the molecular weight of the peak is obtained from the retention time of the chromatogram peak and the molecular weight calibration curve.

  Next, in order to create a calibration curve for performing quantitative calculation, a solution in which the concentration of the standard sample is changed stepwise is used as a standard solution, and the molecular weight distribution measurement method for organic polymer components of the present embodiment described above is used. Perform molecular weight distribution measurement. The standard sample may be used after dissolving in an appropriate aqueous solvent. However, if it is prepared so that the main component concentration is the same as the actual sample, the influence on the analysis result due to the difference in the composition of the sample solution will be reduced. can do. A standard solution to which no organic polymer component such as glue or gelatin is added is a blank measurement, and the background is corrected by subtracting it from other chromatograms. The peak area is obtained from the corrected chromatogram, and a calibration curve is created from the relationship between the concentration and the peak area.

  In this way, a scatter diagram is created based on the gradients of the calibration curves obtained for all the standard samples and the molecular weights of the standard samples, and the relational lines are determined by interpolating the plotted points. This relationship line gives the slope of the calibration curve at each molecular weight included in the molecular weight range of a series of standard samples. Since it is assumed that a straight calibration curve is obtained for each standard sample, a concentration range in which a linear relationship is obtained is confirmed.

  Also, the background of the chromatogram of the actual sample is corrected by subtracting the blank measurement result described above. The chromatogram thus corrected is divided on the horizontal axis, and the peak area for each molecular weight is calculated. For each peak area, the concentration is calculated by C = S / A. In this formula, C is the concentration (mg / L) of the organic polymer component, S is the peak area (absorbance · second), and A is the slope of the calibration curve (absorbance · second · L / mg).

  The molecular weight distribution can be obtained by graphing the relationship between the concentration of the organic polymer component calculated in this way and the molecular weight.

  As an alternative to the pretreatment section shown in FIG. 1, a drainage container 26 is housed in a decompression container 25 connected to an exhaust pipe 24 via a suction pump 23 as shown in FIG. A pipe 28 connected to the outlet side of the lower part of the solid phase cartridge 5 is inserted into the drainage container 26 from the outside of the decompression container 25, and the outlet side of the solid phase cartridge 5 is decompressed by the suction pump 23. Alternatively, required amounts of an organic solvent, water, and a sample solution may be injected into the solid phase cartridge 5 and passed to the upper end.

  Hereinafter, embodiments of the molecular weight distribution measuring apparatus and measuring method for organic polymer components according to the present invention will be described in detail.

[Example 1]
The solid phase cartridge 5 of the molecular weight distribution measuring apparatus for organic polymer components of the above-described embodiment is filled with 50 mg of silica gel having an alkyl group having 18 carbon atoms (particle size: 40 μm, pore size: 50 nm) as a solid phase extractant, This solid phase cartridge 5 was connected to a pipe 6. After passing 1 mL of acetonitrile as an organic solvent through the solid phase cartridge 5 thus connected, 1 mL of water was passed for conditioning, and then the glue was dissolved in a phosphate buffer solution of pH 7.0 to obtain a concentration. 2 mL of the glue solution sample prepared to 0.5 g / L was passed. Next, after washing the solid phase cartridge 5 with 1 mL of pH 7.0 phosphate buffer as a washing solution, 1 mL of eluent consisting of 40% acetonitrile and 60% pH 7.0 phosphate buffer is passed through the solid phase cartridge 5. The glue was eluted and collected in a 10 mL volumetric flask. 0.8 mL of a solution obtained by diluting the obtained eluate with water to a volume of 10 mL was injected by the sample injector 19 into a size exclusion column 21 having an inner diameter of 15 mm, a length of 200 mm, and an exclusion limit molecular weight of 700,000. A chromatogram was prepared by measuring light absorption. A graph in which the horizontal axis of the obtained chromatogram is converted into molecular weight is shown in FIG. In addition, 0.8 mL of a glue solution sample prepared by dissolving glue in a phosphate buffer solution of pH 7.0 to a concentration of 0.1 g / L is directly injected into the size exclusion column 21, and the absorption of light having a wavelength of 210 nm is measured. A chromatogram was created. A graph in which the horizontal axis of the obtained chromatogram is converted into molecular weight is shown in FIG. The glue recovery rate determined from the ratio of the peak area in FIG. 4 to the peak area in FIG. 5 was 93%.

[Comparative Example 1]
The same measurement as in Example 1 was performed except that the solid phase cartridge 5 filled with 50 mg of nonpolar styrene-divinylbenzene resin (particle size 74 to 147 μm, pore size 9 nm) was used as the solid phase extractant. The measurement results are shown in FIG. The glue recovery rate determined from the ratio of the peak area in FIG. 6 to the peak area in FIG. 5 was 44%. According to a comparison between this comparative example and Example 1, when a styrene-divinylbenzene resin is used as the solid phase extractant to be filled in the solid phase cartridge 5, the recovery rate of glue is low, especially the ability to recover glue with a molecular weight of 10,000 or more. Is inferior.

[Comparative Example 2]
The same measurement as in Example 1 was performed except that the solid phase cartridge 5 filled with 50 mg of silica gel having an alkyl group having 8 carbon atoms (particle size: 40 μm, pore size: 6 nm) was used as the solid phase extractant. The measurement results are shown in FIG. The glue recovery rate determined from the ratio of the peak area of FIG. 7 to the peak area of FIG. 5 was 17%. From a comparison between this comparative example and Example 1, it is found that when silica gel having an alkyl group having 8 carbon atoms is used as the solid phase extraction agent to be filled in the solid phase cartridge 5, the recovery ability is inferior.

[Example 2]
The concentration of a standard sample of glue whose molecular weight was measured in advance was changed stepwise and added to a copper electrolyte (copper 40 g / L, nickel 40 g / L, sulfuric acid 200 g / L) to prepare a sample solution for a calibration curve. . Using 10 mL of this sample solution, the molecular weight distribution of the glue was measured by the molecular weight distribution measuring apparatus shown in FIGS. The same solid phase cartridge 5 and size exclusion column 21 as in Example 1 were used. Further, a 0.01 mol / L phosphate buffer (pH 2.5) is used as a washing solution for the solid phase cartridge 5, and a 0.01 mol / L phosphate buffer (pH 7. 5) containing 40% acetonitrile as an eluent. 0) was used. As the mobile phase of the size exclusion column 21, a 0.01 mol / L phosphate buffer containing 0.2 mol / L sodium chloride was used. The volume of the sample loop 20 was 0.6 mL, a peristaltic pump was used as the pump 4 and the pump 9, and a double plunger pump was used as the pump 11 and the pump 18. Moreover, the detection was performed by measuring the absorbance at a wavelength of 210 nm, and a copper electrolyte containing no glue was measured under the same conditions as a blank measurement. Further, after correcting by subtracting the blank measurement chromatogram from the copper electrolyte chromatogram, a calibration curve was prepared from the peak area. The calibration curve was prepared for each glue standard sample having a different molecular weight. The relationship line of FIG. 8 was obtained by graphing the molecular weight of the glue standard sample and the slope of the calibration curve. From this figure, it can be seen that the detection sensitivity of glue varies with the molecular weight.

[Example 3]
In the same manner as in Example 2, the molecular weight distribution of glue was measured using 10 mL of a sample obtained by adding 2 mg / L of glue to a copper electrolyte (copper 40 g / L, nickel 40 g / L, sulfuric acid 200 g / L). . Immediately after the glue was added (after 0 hours) and after heating at 50 ° C. for 2 hours, the sample was measured, and the measurement result was obtained by converting the area into a concentration using the relationship line of Example 2. The molecular weight distribution is shown in FIG. 9 and FIG.

It is a block diagram of the pre-processing part of embodiment of the molecular weight distribution measuring apparatus by this invention. It is a block diagram of the collection | recovery / separation / detection part of embodiment of the molecular weight distribution measuring apparatus by this invention. It is a block diagram of the pre-processing part which can be used instead of the pre-processing part of FIG. It is a figure which shows the measurement result of Example 1 when the eluate of glue is obtained using embodiment of the molecular weight distribution measuring apparatus by this invention shown in FIG. 1 and FIG. It is a figure which shows the measurement result of Example 1 when the glue solution is directly inject | poured into the size exclusion column 21 of embodiment of the molecular weight distribution measuring apparatus by this invention shown in FIG. 1 and FIG. It is a figure which shows the measurement result of the comparative example 1. It is a figure which shows the measurement result of the comparative example 2. FIG. 6 is a diagram showing a relationship line obtained by Example 2. It is a figure which shows the measurement result immediately after the addition of the glue of Example 3. It is a figure which shows the measurement result after adding the glue of Example 3 and heating for 2 hours.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Container (organic solvent), 2 ... Container (water), 3 ... Container (sample solution), 4 ... Pump, 5 ... Solid phase cartridge, 6 ... Piping, 7 ... Piping, 8 ... Container (cleaning liquid), 9 ... Pump 10, container (eluent) 11, pump 12, three-way valve, 13 pipe, 14 pipe, 15 hexagon valve, 16 drain, 17 container (mobile phase), 18 pump, 19 Sample injector, 20 ... sample loop, 21 ... size exclusion column, 22 ... detector, 23 ... suction pump, 24 ... exhaust pipe, 25 ... depressurized container, 26 ... drainage container, 27 ... flow control valve, 28 ... piping

Claims (7)

An organic polymer component collection unit that collects organic polymer components from the sample solution, and a meter recovery unit that measures and collects the eluate of the organic polymer components separated from the organic polymer component collection unit by elution And an organic polymer component separation unit for sequentially separating the eluate of a certain volume of the organic polymer component collected by the weighing and collecting unit according to the molecular weight, and sequentially separating the organic polymer component separation unit according to the molecular weight from the organic polymer component separation unit. And a detection unit that sequentially detects predetermined characteristics of the eluted organic polymer component eluate and obtains the molecular weight distribution of the organic polymer component based on the detected value of the characteristics. A molecular weight distribution measuring device for molecular components. The molecular weight distribution measuring apparatus according to claim 1, wherein the organic polymer component separation unit is a size exclusion column. The molecular weight distribution measuring apparatus for organic polymer components according to claim 1, wherein the weighing and collecting unit is a flow path having a constant volume. The organic polymer component collecting part has a solid-phase extraction agent that collects an organic polymer component from a sample solution and separates the organic polymer component by elution. An apparatus for measuring the molecular weight distribution of an organic polymer component according to claim 1. The molecular weight distribution measuring apparatus for organic polymer components according to claim 4, wherein the solid-phase extractant is a solid-phase extractant having an alkyl group having 18 carbon atoms and a pore diameter of 50 nm. A step of collecting the organic polymer component from the sample solution, a step of separating the collected organic polymer component as an eluent, and a step of measuring and recovering the separated eluate of the organic polymer component And a step of sequentially separating the collected eluate of a certain volume of the organic polymer component according to the molecular weight, and sequentially detecting predetermined characteristics of the eluate of the organic polymer component sequentially separated according to the molecular weight. And obtaining a molecular weight distribution of the organic polymer component based on the detected value of the characteristic. A plurality of standard samples having different molecular weights of the organic polymer component are prepared, and a solution in which the concentration of these standard samples is changed stepwise is used as a standard solution, and each standard sample is classified according to the molecular weight of the organic polymer component. A calibration curve showing the relationship between the concentration of the organic compound and the detected value is created, and a molecular weight distribution is obtained from the relationship between the concentration and molecular weight of the organic polymer component based on the calibration curve, and the organic polymer component is quantified by molecular weight. The method for measuring the molecular weight distribution of an organic polymer component according to claim 6, comprising the step of:

Images