JP2016194490A - Method and system for analyzing hindered amine system photo-stabilizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for analyzing the HALS by simple operations and with excellent quantitative performances.SOLUTION: The method includes the steps of: causing a sample 2 containing a hindered amine-system photo-stabilizer with ester linkage to react with a fluid 3 containing alcohol in a supercritical state or a subcritical state; and identifying the concentration of a decomposition product 5 obtained by the reaction step.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an analysis method and an analysis system for a hindered amine light stabilizer.

  A hindered amine light stabilizer (HALS) is widely used as a stabilizer for improving weather resistance of a resin or the like. However, HALS is difficult to quantitatively analyze because of its low solubility in a solvent and adsorption to a resin and a filler due to an amine skeleton. Therefore, development of a method for quantitatively analyzing HALS is desired.

  Patent Document 1 discloses an analysis method in which HALS in polypropylene is measured by pyrolysis gas chromatography and analyzed by an atomic emission detector.

  Patent Document 2 discloses a method for analyzing HALS in a vinyl chloride resin by using a high-frequency electromagnetic induction device, and this method is performed through the following steps (A) and (B) to modify the HALS. The analysis of the substance.

(A) A resin sample and an extraction solvent are mixed, and the obtained mixed solution is heated by high frequency electromagnetic induction to extract an organic component containing HALS;
(B) The extract is heated by high frequency electromagnetic induction in the presence of methanol or ethanol to denature HALS.

  Non-patent documents 1 and 2 disclose a highly sensitive quantitative analysis method of HALS by reaction thermal desorption gas chromatography. Patent Document 3 discloses a method for recovering a monomer from an aromatic polyester using supercritical methanol.

JP 2000-32258 A (published on November 24, 2000) JP 2010-122151 A (published June 3, 2010) Japanese Patent Laid-Open No. 9-249597 (published September 22, 1997)

Kimura et. Al., Analyst, 125, 465-468, 2000 Taguchi et. Al., J. Chromatogr. A, 993, 137-142, 2003

  However, the conventional techniques as described above have not been sufficient from the viewpoint of analyzing HALS by a simple operation and good quantitativeness.

  For example, Patent Document 1 analyzes the presence and qualitativeness of HALS in polypropylene and does not perform quantitative analysis. Also, Patent Document 2 does not show the results of quantitative analysis. Furthermore, the technique of Patent Document 2 requires complicated operations. Further, Patent Document 3 does not disclose the analysis result of HALS.

  The techniques described in Non-Patent Documents 1 and 2 also require pretreatment such as thermal decomposition with addition of organic alkali, and are complicated.

  The present invention has been made in view of the above-described conventional problems, and an object of the present invention is to provide a method for analyzing HALS by a simple operation and good quantitativeness.

  The present inventors have intensively studied to solve the above problems, and by quantifying a decomposition product obtained by reacting HALS with a fluid under high temperature and high pressure, by simple operation and good quantification. The present inventors have found that HALS can be analyzed and completed the present invention.

  That is, the analysis method according to the present invention is a method for analyzing a hindered amine light stabilizer in order to solve the above-described problem, and includes a fluid containing a sample containing a hindered amine light stabilizer having an ester bond and alcohol. And a reaction step of reacting in a supercritical state or a subcritical state, and a quantitative step of quantifying the concentration of the decomposition product of the hindered amine light stabilizer obtained in the reaction step. .

  In the analysis method according to the present invention, the alcohol may be an alcohol having 1 to 4 carbon atoms.

  In the analysis method according to the present invention, the alcohol may be methanol.

  In the analysis method according to the present invention, the fluid may further include at least one of water and carbon dioxide.

  In the analysis method according to the present invention, the alcohol content in the fluid may be 70 to 90%.

  In the analysis method according to the present invention, the fluid may be a mixture of methanol and water.

  In the analysis method according to the present invention, the decomposition product may be a carboxylic acid ester.

  In the analysis method according to the present invention, in the above-described quantification step, quantification may be performed using gas chromatography mass spectrometry, liquid chromatography mass spectrometry, or gas chromatography with a flame ionization detector.

  The analysis system according to the present invention is an analysis system for hindered amine light stabilizers, wherein a sample containing a hindered amine light stabilizer having an ester bond and a fluid containing alcohol are brought into a supercritical state or a subcritical state. And a reaction part to be reacted, and a quantitative part for quantifying the concentration of the decomposition product of the hindered amine light stabilizer obtained in the reaction part.

  In the analysis system according to the present invention, the alcohol may be an alcohol having 1 to 4 carbon atoms.

  In the analysis system according to the present invention, the alcohol may be methanol.

  In the analysis system according to the present invention, the fluid may further include at least one of water and carbon dioxide.

  In the analysis system according to the present invention, the alcohol content in the fluid may be 70 to 90%.

  In the analysis system according to the present invention, the fluid may be a mixture of methanol and water.

  In the analysis system according to the present invention, the decomposition product may be a carboxylic acid ester.

  In the analysis system according to the present invention, the quantification unit may be a gas chromatograph mass spectrometer, a liquid chromatograph mass spectrometer, or a gas chromatograph device with a flame ionization detector.

  The present invention has an effect that HALS can be analyzed by a simple operation and good quantitativeness.

It is a mimetic diagram showing an analysis system concerning one embodiment of the present invention. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-1. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-2. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-3. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-4. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-5. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-6. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-7. It is a figure which shows the GC-MS TIC chromatogram obtained in this-application Example 5-8.

  Hereinafter, although an example of an embodiment of the invention is explained in detail, the present invention is not limited to these. Unless otherwise specified in this specification, “A to B” indicating a numerical range means “A or more and B or less”.

[1. Analysis method)
The analysis method according to the present invention is a method for analyzing a hindered amine light stabilizer, wherein a sample containing a hindered amine light stabilizer having an ester bond and a fluid containing alcohol are brought into a supercritical state or a subcritical state. A reaction step of reacting with each other, and a quantitative step of quantifying the concentration of the decomposition product of the hindered amine light stabilizer obtained in the reaction step.

<1-1. Reaction process>
This reaction step is a step of reacting a sample containing a hindered amine light stabilizer having an ester bond with a fluid containing alcohol under high temperature and high pressure.

  The hindered amine light stabilizer to be analyzed in the analysis method according to the present invention has an ester bond. Therefore, in the reaction step, the ester bond of the hindered amine light stabilizer can be selectively cleaved, and the resulting decomposition product can be analyzed in the quantitative step described later.

  Although it does not specifically limit as a hindered amine light stabilizer which has the said ester bond, For example, the compound of following formula (I)-(V) is mentioned.

(Here, n represents an integer of 1 or more.)

  The compound of the above formula (I) is Tinuvin (registered trademark) 622 (manufactured by BASF). The compound of the above formula (II) is Tinuvin (registered trademark) 123 (manufactured by BASF). The compound of the above formula (III) is Sanol (registered trademark) LS-2626 (manufactured by Sankyo Lifetech Co., Ltd.). The compound of the above formula (IV) is ADK STAB (registered trademark) LA-52 (manufactured by ADEKA Corporation). The compound of the said formula (V) is ADK STAB (trademark) LA-57 (made by ADEKA Corporation).

  In addition, as a hindered amine light stabilizer having an ester bond, Tinuvin (registered trademark) 144 (manufactured by BASF), Sanol (registered trademark) LS-765 (manufactured by Sankyo Lifetech Co., Ltd.), Sanol (registered trademark) LS-770 (manufactured by Sankyo Lifetech Co., Ltd.), ADK STAB (registered trademark) LA-62 (manufactured by ADEKA Corporation), ADK STAB (registered trademark) LA-63 (manufactured by ADEKA Corporation), ADK STAB (registered trademark) LA-67 (Manufactured by ADEKA Corporation), ADK STAB (registered trademark) LA-68 (manufactured by ADEKA Corporation), and the like.

  The sample containing the hindered amine light stabilizer may be a hindered amine light stabilizer or a composition containing other organic compounds. Although it does not specifically limit as an organic compound which can be contained in the said composition, Polypropylene, polyethylene, nylon, ABS resin (acrylonitrile / butadiene / styrene copolymer) etc. are mentioned.

  Moreover, additives other than a hindered amine light stabilizer may be contained in the composition. According to the analysis method of the present invention, an additive other than the hindered amine light stabilizer is included in the sample in order to quantify the degradation product obtained by selectively cleaving the ester bond of the hindered amine light stabilizer. Even if it is, the hindered amine light stabilizer can be selectively analyzed.

  The fluid is a solvent (reaction solvent) for decomposing the hindered amine light stabilizer. The fluid contains alcohol. Therefore, in the above reaction step, the ester bond of the hindered amine light stabilizer can be selectively cleaved.

  Although the said alcohol is not specifically limited, It is preferable that it is C1-C4 alcohol, and it is more preferable that it is C1-C3 alcohol. If it is the said carbon number, it is preferable from viewpoints, such as practicality and the critical point of alcohol. For example, methanol, ethanol, isopropanol, butanol, etc. are mentioned as said alcohol. Of these, methanol or isopropanol is preferable, and methanol is more preferable. When the alcohol is methanol, it is preferable because it shows particularly good quantitative properties in the quantitative step described later. In the present specification, “good quantification” means that accurate quantification is possible, recovery is high, and reproducibility is also good.

  The fluid may be a fluid made of alcohol and may contain other components. Examples of other components include water and carbon dioxide. For example, the fluid may further include at least one of water and carbon dioxide. In the case where the fluid is a mixture of methanol and water, as shown in the examples described later, particularly good quantitative properties are exhibited, which is preferable.

  The alcohol content in the fluid is preferably 50 to 100% by volume, more preferably 50 to 90% by volume, and particularly preferably 70 to 90% by volume. When the fluid is a mixture of methanol and water, the methanol / water mixing ratio (volume ratio) is preferably 50/50 to 900/10, and more preferably 70/30 to 90/10. preferable.

  When the alcohol content is 50 to 90%, the recovery rate is high and preferable. In addition, it is preferable that the alcohol content is 70% or more because the quantitative value and / or the recovery rate is stable and the reproducibility is good. In particular, when GC-MS is used in the quantitative step described later, the alcohol content is preferably 70 to 100%, more preferably 70 to 90%, from the viewpoint of obtaining good quantitative properties.

  A decomposition product of the hindered amine light stabilizer can be obtained by reacting the sample containing the hindered amine light stabilizer with the fluid under a high temperature and high pressure described later. The decomposition product is generated by cleaving the ester bond of the hindered amine light stabilizer. Examples of the decomposition products include carboxylic acid esters and amines.

  As a decomposition product obtained when a sample containing the compound of the above formula (I) is reacted with a fluid containing methanol, for example, a compound of the following formula (a) which is a carboxylic acid ester and an amine which is the following: A compound of the formula (b) can be mentioned.

  The compound of the above formula (a) is dimethyl succinate. Here, for example, when the compound of the above formula (I) is reacted with a fluid containing isopropanol, diisopropyl succinate is obtained.

  Examples of decomposition products obtained when a sample containing the compound of the formula (II) is reacted with a fluid containing methanol include, for example, compounds of the following formulas (c) to (f) which are amines, carboxylic acids Examples thereof include compounds of the following formulas (g) and (h) which are esters, and octene isomers.

  As a decomposition product obtained when a sample containing the compound of the above formula (III) is reacted with a fluid containing methanol, for example, in addition to the compound of the above formula (e) which is an amine, the following which is an amine: Examples include compounds of the formulas (i) and (j), and compounds of the following formulas (k) to (o) which are carboxylic acid esters.

  Examples of decomposition products obtained when a sample containing the compound of formula (IV) or (V) is reacted with a fluid containing methanol include, for example, amines of the above formulas (c), (d) and In addition to the compound of (f), the compound of the following formula (p) which is carboxylic acid ester, and the compound of the following formula (q) are mentioned.

  Of course, the decomposition product of the hindered amine light stabilizer is not limited to these, and various compounds can be obtained depending on the structure of the hindered amine light stabilizer and the alcohol.

The reaction step can be performed, for example, by putting a sample containing a hindered amine light stabilizer and a fluid containing alcohol in a container and sealing it, and then heating the sealed container. The internal volume of the sealed container is not particularly limited, and may be appropriately set according to the amount of the sample containing the hindered amine light stabilizer and the fluid containing alcohol. Interior volume of the container, for example, may be a 0.1～0.5Cm ^3, may be 0.5 to 1.0 cm ^3, may be 1.0~1.5cm ^3.

The amount of fluid put in the sealed container is not particularly limited, and can be appropriately set according to the internal volume of the container. For example, when the internal volume of the container is 0.1 to 0.5 cm ³ , the amount of fluid is preferably 20 to 200 μL, and more preferably 35 to 180 μL. Moreover, when the internal volume of a container is 0.5-1.0 cm < ³ >, it is preferable that the quantity of a fluid is 150-400 microliter, and it is more preferable that it is 180-360 microliter. When the internal volume of the container is 1.0 to 1.5 cm ³ , the amount of fluid is preferably 300 to 600 μL, and more preferably 360 to 540 μL. If it is said amount, reaction can be advanced efficiently.

Moreover, the quantity of the sample containing a hindered amine light stabilizer is not specifically limited, It can set suitably according to the internal volume of the said container. For example, when the internal volume of the container is 0.1 to 0.5 cm ³ , the amount of the sample is preferably 2 to 13 mg, and more preferably 2 to 11 mg. Moreover, when the internal volume of a container is 0.5-1.0 cm < ³ >, it is preferable that the quantity of a sample is 9-25 mg, and it is more preferable that it is 11-22 mg. When the internal volume of the container is 1.0 to 1.5 cm ³ , the amount of the sample is preferably 20 to 50 mg, and more preferably 22 to 45 mg. If it is said amount, reaction can be advanced efficiently.

  The material of the said container is not specifically limited, What is necessary is just to have heat resistance while being able to make internal space high temperature. In the container, for example, the inner wall surface of the container may be made of nickel alloy, gold alloy, magnesium alloy, cobalt alloy, aluminum alloy, copper alloy, alloy steel, or iron alloy. As the container, it is possible to use a commonly used SUS container.

  The sample containing the hindered amine light stabilizer and the fluid are reacted in a supercritical state or a subcritical state. In this specification, the supercritical state means a state under high temperature and high pressure exceeding the critical point of the alcohol contained in the fluid, the critical temperature means the temperature at the critical point of the alcohol, and the critical pressure is It means the pressure at the critical point of the alcohol. In the present specification, the critical point means a point where a boundary between a gas phase and a liquid phase of a substance disappears. Further, in the present specification, the subcritical state means a state in which at least one of temperature and pressure is not higher than the critical point but is under high temperature and high pressure. Specifically, the subcritical state means that the temperature is above the boiling point on the alcohol vapor pressure curve and below the critical temperature, and / or the pressure is above the pressure at the boiling point on the alcohol vapor pressure curve and below the critical pressure. To do.

  The reaction temperature at which the sample containing the hindered amine light stabilizer reacts with the fluid may be a temperature at which the alcohol contained in the fluid becomes a supercritical state or a subcritical state. The temperature is preferably + 200 ° C, more preferably critical temperature to critical temperature + 150 ° C, and particularly preferably critical temperature + 50 ° C to critical temperature + 100 ° C. Further, the pressure for reacting the sample containing the hindered amine light stabilizer and the fluid may be a pressure at which the alcohol contained in the fluid becomes a supercritical state or a subcritical state, and is from critical pressure to critical pressure + 15 MPa. The critical pressure is preferably critical pressure to critical pressure + 10 MPa, and more preferably critical pressure + 2 MPa to critical pressure + 8 MPa. When using the above-described container, heating may be performed so that the inside of the container reaches the reaction temperature.

  If it is the said reaction conditions, the fluid containing alcohol can be made into a supercritical state or a subcritical state. Therefore, the sample containing the hindered amine light stabilizer and the fluid can be reacted efficiently.

  For example, the critical temperature of methanol is 239 ° C. and the critical pressure is 8.1 MPa. Accordingly, the reaction temperature when the fluid contains methanol is preferably 200 to 439 ° C, more preferably 239 to 389 ° C, and further preferably 289 to 339 ° C. When the fluid contains methanol, the reaction pressure is preferably 8.1 to 18.1 MPa, more preferably 10.1 to 16.1 MPa. The critical temperature of isopropanol is 235 ° C., and the critical pressure is 5.37 MPa. Therefore, the reaction temperature when the fluid contains isopropanol is preferably 200 to 435 ° C, more preferably 235 to 385 ° C, and further preferably 285 to 335 ° C. When the fluid contains isopropanol, the reaction pressure is preferably 5.4 to 19.3 MPa, more preferably 8.3 to 17.3 MPa, and preferably 10.3 to 15.3 MPa. Further preferred. The critical temperature of water is 374 ° C., and the critical pressure is 22 MPa. Considering that the fluid is a mixture, the reaction temperature may be 300 to 400 ° C., and the reaction pressure may be 10 MPa or more.

  In the said reaction process, it is good also as the said reaction temperature, after heating up gradually from 100-200 degreeC. The rate of temperature increase may be, for example, 10 to 30 ° C./min or 15 to 25 ° C./min. Moreover, after reaching the reaction temperature, it is preferable to hold for 30 to 180 minutes, and more preferably 60 to 120 minutes. According to the said conditions, reaction can fully be advanced. According to the analysis method of the present invention, pretreatment and measurement can be completed in a few hours. That is, according to the analysis method of the present invention, the analysis can be performed in an extremely short time as compared with the prior art.

  The configuration for heating the container is not particularly limited, and a known heater, incinerator, sand bath, or the like may be used as appropriate. Moreover, in order to heat a container, you may use oven etc. of a gas chromatograph apparatus.

  After holding for a predetermined time at the reaction temperature, after cooling to room temperature, the obtained decomposition product may be used in a quantitative step described later.

  In the reaction step, the sample containing the hindered amine light stabilizer and the fluid are simply reacted under high temperature and high pressure. And the said reaction process is realizable by putting and heating the sample containing the said hindered amine light stabilizer and the said fluid in a container, for example. That is, the analysis method of the present invention can be carried out by a simple operation as compared with the prior art that requires complicated pretreatment.

<1-2. Determination process>
The said determination process is a process of quantifying the density | concentration of the decomposition product of the said hindered amine light stabilizer obtained in the said reaction process.

  As described above, carboxylic acid esters, amines and the like are obtained as decomposition products. In the quantification step, all of the obtained degradation product may be used, or a part thereof may be used. In addition, in the said determination process, since analysis can be performed with more favorable quantitative property, when carboxylic acid ester is used, it is preferable.

  The quantification method used in the quantification step can be appropriately selected according to the type of the decomposition product and the type of fluid used as the reaction solvent. For example, the quantification step can be performed by gas chromatography mass spectrometry (GC-MS), liquid chromatography mass spectrometry (LC-MS), gas chromatography with a flame ionization detector (GC-FID), or the like. Among these, quantification by GC-MS is preferable from the viewpoint that the analysis target range is wide and that trace components can be detected by SIM measurement.

  Since these quantification methods are techniques well known to those skilled in the art, detailed description thereof is omitted. For example, a calibration curve is first created using a standard product of a hindered amine light stabilizer, and then the sample to be quantified is analyzed to measure the concentration of the hindered amine light stabilizer.

  In the above quantification method, selected ion monitoring (SIM) may be used. In this case, a part of the decomposition product may be used as the selected ion, and for example, a carboxylic acid ester may be used. For example, when the compound of the above formula (I) is reacted with a fluid containing methanol, dimethyl succinate may be used as a selected ion. Further, when the compound of the above formula (I) is reacted with a fluid containing isopropanol, diisopropyl succinate may be used as a selected ion.

  The analysis method of the present invention performs quantification on the degradation product obtained as a result of cleaving the ester bond of the hindered amine light stabilizer in the above reaction step. Therefore, the hindered amine light stabilizer can be analyzed with better quantitativeness than the conventional technique.

[2. Analysis system)
The analysis system according to the present invention will be described below with reference to FIG. The analysis system according to the present invention is the above [1. This is a system for carrying out the method described in the column “Analysis method”. Therefore, the description of the overlapping configuration is omitted here.

  The analysis system according to the present invention is an analysis system for hindered amine light stabilizers, which comprises a sample 2 containing a hindered amine light stabilizer having an ester bond and a fluid 3 containing alcohol in a supercritical state or a subcritical state. The reaction part 4 made to react in a state, and the fixed_quantity | quantitative part 6 which quantifies the density | concentration of the decomposition product 5 of the hindered amine light stabilizer obtained in the reaction part 4 are provided.

<2-1. Reaction part>
The configuration of the reaction unit 4 is not particularly limited as long as the sample 2 containing the hindered amine light stabilizer and the fluid 3 containing the alcohol can be reacted in a supercritical state or a subcritical state.

  Here, the sample 2 and the fluid 3 may be placed in the container 1. The container 1 may have any configuration that can be heated after the sample 2 and the fluid 3 are sealed in the container 1. As the container 1, <1-1. The container described in the reaction step> can be used. As shown in FIG. 1, the container 1 in which the sample 2 and the fluid 3 are placed is stored in the reaction unit 4 and then heated by the reaction unit 4.

  As the reaction part 4, it is <1-1. The “configuration for heating the container” described in the reaction step> can be used. That is, as the reaction unit 4, a known heater, an incinerator, a sand bath, a gas chromatograph apparatus oven, or the like can be used. Conditions such as reaction temperature in the reaction section 4 are the above-described <1-1. The reaction conditions described in the reaction step> can be used.

  By reacting the sample 2 and the fluid 3 in the reaction unit 4, the ester bond of the hindered amine light stabilizer can be selectively cleaved. As a result, the decomposition product 5 of a hindered amine light stabilizer can be obtained.

  In the reaction unit 4, the sample 2 and the fluid 3 are merely reacted at high temperature and high pressure. Specifically, in the reaction unit 4, for example, the reaction can be realized by heating the container 1 containing the sample 2 and the fluid 3. In other words, the analysis system of the present invention can perform analysis with a simple operation compared to the prior art that requires complicated preprocessing.

  Further, according to the analysis system of the present invention, preprocessing and measurement can be completed in a few hours. That is, according to the analysis system of the present invention, the analysis can be performed in a very short time compared to the prior art.

<2-2. Quantitative Section>
In the quantification unit 6, the concentration of the decomposition product 5 of the hindered amine light stabilizer obtained in the reaction unit 4 is quantified.

  The quantification unit 6 is configured as described in <1-2. If it is the structure which can perform the fixed_quantity | assay method demonstrated by fixed_quantity | assay process>, it will not specifically limit. That is, as the quantification unit 6, for example, a gas chromatograph mass spectrometer, a liquid chromatograph mass spectrometer, a gas chromatograph apparatus with a flame ionization detector, or the like can be used. Among these, from the viewpoint that the analysis target range is wide and trace components can be detected by SIM measurement, the quantification unit 6 is preferably a gas chromatograph mass spectrometer.

  The analysis system of the present invention performs quantification on the decomposition product 5 obtained as a result of cleaving the ester bond of the hindered amine light stabilizer in the reaction unit 4 described above. Therefore, the hindered amine light stabilizer can be analyzed with better quantitativeness than the conventional technique.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated according to an Example, this invention is limited to an Example and is not interpreted.

[Example 1. (Investigation of reaction conditions)
The reaction conditions of the analysis method of the present invention were examined using Tinuvin 622 which is one of HALS.

(Example 1-1)
First, a calibration curve was prepared using a standard product of Tinuvin 622. To a SUS tube (outer diameter ¼ ″ (6.25 mm), wall thickness 1.24 mm, length 10 cm, manufactured by Nishio Kogyo Co., Ltd.), 5 mg of Tinuvin 622 standard product and 400 μL of reaction solvent (methanol) In addition, the SUS tube was sealed. The SUS tube was placed in an oven for gas chromatography (manufactured by Shimadzu Corporation), heated from 100 ° C. to 300 ° C. at 20 ° C./min, and held for 60 minutes. Thereafter, the SUS tube was cooled to room temperature and opened. The obtained decomposition reaction solution was made up to 5 mL with methanol (1000 μg / mL). The obtained diluted solution was further diluted 10 times (100 μg / mL). Further, the obtained diluted solution was further diluted 10 times (10 μg / mL). Using these diluted solutions, GC-MS measurement was performed according to a conventional method to prepare a calibration curve. Note that dimethyl succinate was used as the SIM selective ion.

  Next, analysis was performed using a sample having a known concentration of Tinuvin 622. To the SUS tube, 25 mg of Tinuvin 622-containing polypropylene (Tinvin 622 content: 0.15 wt%) and 400 μL of a reaction solvent (methanol) were added, and the SUS tube was sealed. The SUS tube was placed in a gas chromatography oven, heated from 100 ° C. to 300 ° C. at 20 ° C./min, and held for 60 minutes. Thereafter, the SUS tube was cooled to room temperature and opened. GC-MS measurement was performed on the above-mentioned conditions using the obtained decomposition reaction liquid. The measurement was repeated 4 times.

(Example 1-2)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that the reaction solvent (methanol / water = 70/30) was used. The measurement was repeated three times.

(Example 1-3)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that the reaction solvent (isopropanol) was used and diisopropyl succinate having m / z = 101 was used as the SIM selective ion. . The measurement was repeated three times.

(Example 1-4)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that the hold time during decomposition was 120 minutes. The measurement was repeated three times.

(result)
The results of Examples 1-1 to 1-4 are shown in Table 1.

  Under any condition, a recovery rate exceeding 70% was obtained. In particular, Example 1-2 using a reaction solvent (methanol / water = 70/30) showed a high recovery rate.

[Example 2. Study of reaction solvent)
In the analysis method of the present invention, analysis was performed using a sample having a known Tinuvin 622 concentration and changing the mixing ratio of methanol / water.

(Example 2-1)
GC-MS measurement was performed under the same conditions as in Example 1-1.

(Example 2-2)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a methanol / water mixing ratio of 90/10 was used.

(Example 2-3)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a mixing ratio of methanol / water of 80/20 was used.

(Example 2-4)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a methanol / water mixing ratio of 70/30 was used.

(Example 2-5)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a methanol / water mixing ratio of 60/40 was used. The measurement was repeated twice.

(Example 2-6)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a methanol / water mixing ratio of 50/50 was used. The measurement was repeated twice.

(result)
The results of Examples 2-1 to 2-6 are shown in Table 2.

  When the ratio of methanol was 70% or more, the quantitative value was accurate, the recovery rate was close to 100%, and there was little variation. In addition, when the ratio of methanol was 70% or more and 90% or less compared to a fluid having 100% methanol, it was possible to quantify more accurately and the recovery rate was 100%.

[Example 3. (Reproducibility study)
The GC-MS measurement was performed several times using the analysis method of the present invention, and reproducibility was confirmed.

(Example 3-1)
GC-MS measurement was performed under the same conditions as in Example 1-1. The measurement was repeated 4 times.

(Example 3-2)
GC-MS measurement was performed under the same conditions as in Example 1-1 except that a reaction solvent having a methanol / water mixing ratio of 70/30 was used. The measurement was repeated three times.

(result)
The results of Examples 3-1 to 3-2 are shown in Table 3.

  From the above results, it was found that stable reproducibility was exhibited in any of Examples 3-1 and 3-2. Moreover, compared with the case where only methanol was used as the reaction solvent, the recovery rate was improved when the reaction solvent having a methanol / water mixing ratio of 70/30 was used.

[Example 4. Examination of sample generality)
In the analysis method of the present invention, analysis was performed using a sample having a known Tinuvin 622 concentration and further containing an additive other than HALS.

(Example 4-1)
Example 1-1, except that Tinuvin 622-containing polypropylene (Tinvin 622 content: 0.15 wt%, Irganox (registered trademark) 1010 (BASF) content: 0.05 wt%) was used as a sample. GC-MS measurement was performed under conditions.

(Example 4-2)
Tinuvin 622-containing polypropylene (Tinuvin 622 content: 0.15 wt%, Irganox 1010 content: 0.05 wt%, Irgafos (registered trademark) 168 (BASF) content: 0.05 wt%) was used as a sample. Except for the above, GC-MS measurement was performed under the same conditions as in Example 1-1.

(Example 4-3)
Example 1 except that Tinuvin 622-containing polypropylene (Tinuvin 622 content: 0.15 wt%, Sumilizer (registered trademark) GA-80 (Sumitomo Chemical Co., Ltd.) content: 0.05 wt%) was used as a sample. GC-MS measurement was performed under the same conditions as in 1.

(Example 4-4)
Example 1-1 except that Tinuvin 622-containing polypropylene (Tinuvin 622 content: 0.15 wt%, Sumilizer GA-80 content: 0.05 wt%, Irgafos 168 content: 0.05 wt%) was used as a sample. GC-MS measurement was performed under the same conditions as those described above.

(Example 4-5)
Example 1-1 with the exception that Tinuvin 622-containing polypropylene (Tinuvin 622 content: 0.15 wt%, Sumizer (registered trademark) GP content (manufactured by Sumitomo Chemical Co., Ltd.): 0.05 wt%) was used as a sample. GC-MS measurement was performed under the same conditions.

(result)
The results of Examples 4-1 to 4-5 are shown in Table 3.

  From the above results, it was found that the analysis method of the present invention can collect and quantify a specific analysis target additive (HALS) even when a sample containing various additives is used.

In addition, the lower limit of quantification and linearity were calculated. The lower limit of quantification was determined by the following formula (1) and further expressed in wt%.
Quantitative value (μg / g) = concentration in measurement solution (μg / mL) × constant volume (mL) / sample amount (g) (1)
Here, the concentration in the measurement solution (detection lower limit concentration) was 10 μg / mL, the constant volume was 0.4 mL (to measure the decomposition solution stock solution), and the sample amount was 0.025 g.

  The linearity was determined as a correlation coefficient for this calibration curve by preparing a 3-check calibration curve using a standard solution diluted 10-fold and 100-fold in the same manner as in Example 1-1.

In this case, the lower limit of quantification was 0.016% by weight, and the linearity was R ² = 1.000. Therefore, it was found that the analysis method of the present invention has good sample generality and linearity.

[Example 5. Application to other HALS]
In the analysis method of the present invention, analysis was performed using HALS other than Tinuvin 622.

(Example 5-1)
Analysis was performed using a standard product of Sanol LS-2626 as a sample. To a SUS tube (outer diameter 1/4 ″ (6.25 mm), wall thickness 1.24 mm, length 10 cm, manufactured by Nishio Kogyo Co., Ltd.), Sanol LS-2626 standard product 13 mg, reaction solvent (methanol) 400 μL, And the SUS tube was sealed. The SUS tube was placed in an oven for gas chromatography (manufactured by Shimadzu Corporation), heated from 100 ° C. to 300 ° C. at 20 ° C./min, and held for 60 minutes. Thereafter, the SUS tube was cooled to room temperature and opened. GC-MS measurement was performed according to a conventional method using the obtained decomposition reaction solution.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 2, peak A is the compound of the above formula (e), peak B is the compound of the above formula (i), peak C is the compound of the above formula (j), peak D is the compound of the above formula (l), peak E Represents a compound of the above formula (m).

(Example 5-2)
GC-MS measurement was performed under the same conditions as in Example 5-1, except that a reaction solvent having a methanol / water mixing ratio of 70/30 was used.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 3, peak A is the compound of the above formula (e), peak B is the compound of the above formula (i), peak C is the compound of the above formula (k), peak D is the compound of the above formula (l), peak E Represents the compound of the above formula (m), the peak F represents the compound of the above formula (n), and the peak G represents the compound of the above formula (o).

(Example 5-3)
GC-MS measurement was performed under the same conditions as in Example 5-1, except that a standard product of Tinuvin 123 was used as a sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 4, peak A is the octene isomer, peak B is the compound of the above formula (c), peak C is the compound of the above formula (d), peak D is the compound of the above formula (e), and peak E is the above formula ( The compound of f) and the peak F show the compound of the above formula (g).

(Example 5-4)
GC-MS measurement was performed under the same conditions as in Example 5-2 except that a standard product of Tinuvin 123 was used as a sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 5, peak A is the octene isomer, peak B is the compound of the above formula (c), peak C is the compound of the above formula (d), peak D is the compound of the above formula (e), and peak E is the above formula ( The compound of g) and the peak F indicate the compound of the above formula (h).

(Example 5-5)
GC-MS measurement was performed under the same conditions as in Example 5-1, except that a standard product of ADK STAB LA-52 was used as a sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 6, peak A represents the compound of the above formula (c), peak B represents the compound of the above formula (d), peak C represents the compound of the above formula (f), and peak D represents the compound of the above formula (p). Yes.

(Example 5-6)
GC-MS measurement was performed under the same conditions as in Example 5-2, except that ADK STAB LA-52 standard was used as a sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 7, peak A represents the compound of the above formula (c), peak B represents the compound of the above formula (d), peak C represents the compound of the above formula (f), and peak D represents the compound of the above formula (p). Yes.

(Example 5-7)
GC-MS measurement was performed under the same conditions as in Example 5-1, except that a standard product of ADK STAB LA-57 was used as a sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. In FIG. 8, peak A represents the compound of the above formula (c), peak B represents the compound of the above formula (d), peak C represents the compound of the above formula (f), and peak D represents the compound of the above formula (p). Yes.

(Example 5-8)
The GC-MS measurement was performed under the same conditions as in Example 5-2 except that the standard product of ADK STAB LA-57 was used as the sample.

  The obtained GC-MS TIC chromatogram is shown in FIG. 9, peak A is the compound of the above formula (c), peak B is the compound of the above formula (d), peak C is the compound of the above formula (f), peak D is the compound of the above formula (q), peak E Represents a compound of the above formula (p).

(result)
As shown in FIGS. 2 to 9, it was found that HALS other than Tinuvin 622 can also be decomposed by the analysis method of the present invention, and decomposed products can be analyzed. Moreover, if these decomposition products are used, it is also possible to perform a quantitative analysis. For example, quantitative analysis can be performed by performing GC-MS using a carboxylic acid ester as a selected ion among the decomposed products.

[Example 6. Reaction in subcritical state)
In the analysis method of the present invention, the reaction process was performed in a subcritical state, and the analysis was performed.

(Example 6-1)
The reaction solvent having a methanol / water mixing ratio of 70/30 was used, and the SUS tube was placed in an oven for gas chromatography, and the temperature was raised from 100 ° C. to 200 ° C. at 20 ° C./min. The GC-MS measurement was performed under the same conditions as in Example 1-1 except that the hold was performed for 60 minutes.

(Example 6-2)
The GC-MS was placed under the same conditions as in Example 6-1 except that the SUS tube was placed in a gas chromatography oven, heated from 100 ° C. to 220 ° C. at 20 ° C./min, and held for 60 minutes. Measurements were made.

(result)
The results of Examples 6-1 and 6-2 are shown in Table 5.

  From the above results, it was confirmed that the reaction proceeded even in the subcritical state and analysis was possible. It was confirmed that the recovery rate increased as the reaction temperature increased.

  The present invention can be widely used for analysis of HALS in resins used in various fields.

DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Sample 3 ... Fluid 4 ... Reaction part 5 ... Decomposition product 6 ... Determination part

Claims (16)

A method for analyzing a hindered amine light stabilizer,
A reaction step of reacting a sample containing a hindered amine light stabilizer having an ester bond and a fluid containing alcohol in a supercritical state or a subcritical state;
A quantitative step of quantifying the concentration of the degradation product of the hindered amine light stabilizer obtained in the reaction step.   The analysis method according to claim 1, wherein the alcohol is an alcohol having 1 to 4 carbon atoms.   The analysis method according to claim 2, wherein the alcohol is methanol.   The analysis method according to claim 1, wherein the fluid further contains at least one of water and carbon dioxide.   The analysis method according to claim 4, wherein the content of alcohol in the fluid is 70 to 90%.   6. The analysis method according to claim 4, wherein the fluid is a mixture of methanol and water.   The analytical method according to claim 1, wherein the decomposition product is a carboxylic acid ester.   8. The quantitative determination according to claim 1, wherein the quantitative determination is performed using gas chromatography mass spectrometry, liquid chromatography mass spectrometry, or gas chromatography with a hydrogen flame ionization detector. Analysis method. A hindered amine light stabilizer analysis system,
A reaction section for reacting a sample containing a hindered amine light stabilizer having an ester bond with a fluid containing alcohol in a supercritical state or a subcritical state;
And a quantitative unit for quantifying the concentration of the degradation product of the hindered amine light stabilizer obtained in the reaction unit.   The analysis system according to claim 9, wherein the alcohol is an alcohol having 1 to 4 carbon atoms.   The analysis system according to claim 10, wherein the alcohol is methanol.   The analysis system according to any one of claims 9 to 11, wherein the fluid further includes at least one of water and carbon dioxide.   The analysis system according to claim 12, wherein the content of alcohol in the fluid is 70 to 90%.   14. The analysis system according to claim 12, wherein the fluid is a mixture of methanol and water.   The analysis system according to claim 9, wherein the decomposition product is a carboxylic acid ester.   The analysis system according to any one of claims 9 to 15, wherein the quantitative unit is a gas chromatograph mass spectrometer, a liquid chromatograph mass spectrometer, or a gas chromatograph apparatus with a flame ionization detector.

Images