WO2020076075A1 - Qualitative and quantitative analysis method for high molecular weight additive by using size-exclusion chromatography-pyrolysis-gas chromatography/mass spectrometry - Google Patents

Abstract

The present invention relates to a method for securing qualitative and quantitative information of a high molecular weight additive in a polymer resin by using consecutively connected size-exclusion chromatography (SEC)-pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS), and an analysis system used therefor. By analyzing a high molecular weight additive having a specific residue by pyrolyzing the high molecular weight additive into a low molecular weight compound, the present invention can secure the structure and content analysis information of the high molecular weight additive, which were difficult to secure by means of conventional analysis methods.

Description

Qualitative and quantitative analysis of high molecular weight additives using size exclusion chromatography-pyrolysis-gas chromatography / mass spectrometry

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0120966 filed on October 11, 2018 and Korean Patent Application No. 10-2019-0124406 filed on October 8, 2019, above All contents disclosed in the patent document are included as part of the present specification.

The present invention relates to a qualitative and quantitative analysis method of a high molecular weight additive in a polymer resin, and an analytical system used therein, more specifically, continuously connected size exclusion chromatography (SEC) -pyrolysis-gas chromatography / mass spectrometer ( Py-GC / MS) relates to a method for obtaining qualitative and quantitative information of a high molecular weight additive in a polymer resin and an analysis system used therein.

In general, additives in polymer resins are further separated by gas or liquid chromatography after pretreatment such as solvent extraction, soxhlet extraction, and reprecipitation, and structured through spectral analysis. Conduct the analysis. However, in the case of the solvent extraction method, it takes a lot of time and manpower to use an excessive amount of solvent and to determine an appropriate analytical process for each polymer material. In addition, in the case of a high molecular weight additive, due to its large molecular weight and large molecular structure, it is sometimes difficult to easily obtain composition information by chromatography, and in such a case, MALDI-TOF MS (matrix assisted laser desorption ionization-time of flight mass) Although additional experiments using spectrometry or 2-dimensional nuclear magnetic resonance (NMR) spectroscopy are attempted to secure compositional information, it is difficult to obtain compositional information in case of low additive content or mixture It is difficult and the accuracy of quantitative information is poor.

Therefore, it is possible to secure structural analysis results of high molecular weight additives that were not easy to secure analysis information by analyzing conventional chromatography, MALDI-TOF MS, NMR spectroscopy, etc., and measure the content of high molecular weight additives in polymer resins. There is a need to develop an existing method.

An object of the present invention is to provide a qualitative and quantitative analysis method of a high molecular weight additive that was not easy to perform qualitative and quantitative analysis by conventional chromatography, MALDI-TOF MS, NMR spectroscopy, and the like.

To achieve the above object, the present invention is a high molecular weight additive, specifically, piperidine (piperidine), morpholine (morpholine), such as a high molecular weight additive containing a high molecular weight additive having a residue (moiety) chromatography chromatography (SEC) is introduced to separate high molecular weight additives, and the separated high molecular weight additives are introduced into a pyrolysis-gas chromatography / mass spectrometer (Py-GC / MS) to decompose into relatively low molecular weight compounds. By detecting fragment peaks derived from residues such as piperidine and morpholine, qualitative information of a high molecular weight additive is obtained, and quantitative information of a high molecular weight additive is obtained based on the sum of the areas of the fragment peaks. Provides a method.

In addition, the present invention provides an analysis system used for qualitative and quantitative analysis of high molecular weight additives in polymer resins, including size exclusion chromatography, sample collection and automatic injectors, pyrolysis, and gas chromatography / mass spectrometry. .

According to the present invention, by detecting and using fragment peaks derived from the residue in the mass spectrometry spectrum obtained by thermally decomposing a polymer resin containing a high molecular weight additive having a residue such as piperidine, morpholine, etc. with a low molecular weight compound Qualitative and quantitative analysis of the high molecular weight additive is possible.

Figure 1 shows the total ion chromatogram (TIC) (b) and mass spectrum (MS) (c) as SEC data (a) and Py-GC / MS data of Chimasorb ^R 2020 standard and Nylon-6 sample.

2 shows an estimated structure of Chimasorb ^R 2020 based on characteristic m / z values.

Figure 3 is SEC data (a) of Chimasorb ^R 119 standard, total ion chromatography (TIC) (b) and mass spectrum (MS) (c) as Py-GC / MS data, and structure (d) of Chimasorb ^R 119 It shows.

Figure 4 is SEC data (a) of the Cyasorb ^R UV 3345 standard, total ion chromatography (TIC) (b) and mass spectrum (MS) (c) as Py-GC / MS data, and the structure of Cyasorb ^R UV 3345 ( d).

FIG. 5 shows Py-GC / MS selected ion monitoring (SIM) data (a) and characteristic peak mass spectrometry spectrum (b) of the Chimasorb ^R 2020 standard and Nylon-6 samples by concentration.

6 is a calibration line showing the peak area (count) for the concentration of Chimasorb ^R 2020 standard.

Figure 7 shows the mass spectrometry obtained with MALDI-TOF MS for the Nylon-6 sample.

FIG. 8 shows the ¹ H NMR spectrum (a) and the 2D ¹ H- ¹³ C heteronuclear single quantum correlation (HSQC) spectrum (b) obtained for the Nylon-6 sample and the additive standard.

Hereinafter, the present invention will be described in detail.

The present invention is intended to exemplify certain embodiments, as various transformations can be applied and various embodiments can be applied. However, this is not intended to limit the present invention to a specific embodiment, it should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In the description of the present invention, when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted.

In the prior art, the high molecular weight additive in the polymer resin was difficult to obtain composition information easily by chromatography due to its large molecular weight and macromolecular structure, and it was also analyzed through additional experiments using MALDI-TOF MS or 2D nuclear magnetic resonance spectroscopy. It was not easy to secure. Accordingly, there is a need for an analysis method capable of securing qualitative and quantitative analysis results of high molecular weight additives in a polymer resin.

In the present invention, SEC-Py-GC / MS system is used to secure SEC-Py-GC / MS data of high molecular weight additives among polymer resins, and based on this, polymer resins containing high molecular weight additives to be analyzed are of low molecular weight. It provides an analytical method and an analytical system that can be used to secure qualitative and quantitative analysis results of the high molecular weight additive by detecting it by pyrolysis with a compound.

Specifically, the present invention relates to a method for analyzing a high molecular weight additive containing a moiety such as piperidine, morpholine, etc. in a polymer resin sample, wherein the analysis method includes the following steps do:

(1) separating the high molecular weight additive by introducing the sample into size exclusion chromatography (SEC);

(2) introducing the separated high molecular weight additive to pyrolysis-gas chromatography / mass spectrometry (Py-GC / MS) to obtain a mass spectrometry spectrum;

(3) qualitative analysis by detecting fragment peaks derived from residues such as piperidine and morpholine in the mass spectrometry spectrum; And

(4) Quantitative analysis based on the sum of the areas of the fragment peaks.

According to the present invention, first, a specific fraction corresponding to the high molecular weight additive among fractions generated by introducing a high molecular weight additive containing residues such as piperidine and morpholine into SEC in the polymer resin sample is Py-GC / Introduced to Microsoft. The thermally decomposed fraction shows a large number of peaks as a result of GC, and among them, characteristic peaks are detected to obtain a mass spectrometry spectrum. The characteristic fragment peaks identified in the mass spectrometry spectrum are derived from residues such as piperidine and morpholine of the high molecular weight additive, and the m / z value of each peak is compared with the characteristic m / z value of a standard product. The structure of the additive can be confirmed. Subsequently, the area of the fragment peaks in the mass spectrometry spectrum is summed and quantitatively analyzed by substituting it into a calibration line representing the peak area for the concentration of the standard product.

In one embodiment, the molecular weight of the high molecular weight additive may be 1,000 to 4,000 g / mol, in particular 1,300 to 3,500 g / mol.

In one embodiment, the high molecular weight additive is a hindered amine light stabilizer (HALS).

In one embodiment, the hindered amine light stabilizer may be Chimasorb ^R 2020, Chimasorb ^R 119 and Cyasorb ^R UV 3345.

In one embodiment, the high molecular weight additive is Chimasorb ^R 2020, and characteristic fragment peaks comprising its piperidine residue appear at m / z 58, 98, 124 and 140.

In one embodiment, the high molecular weight additive is Chimasorb ^R 119, and characteristic fragment peaks comprising its piperidine residue appear at m / z 58, 98, 124, 140 and 152.

In one embodiment, the high molecular weight additive is Cyasorb ^R UV 3345, and characteristic fragment peaks comprising its morpholine residues appear at m / z 58, 98, 124, 138, 267, 279 and 336.

In one embodiment, the high molecular weight additive may be contained in an amount of 0.3 to 0.7% by weight based on the weight of the polymer resin.

In one embodiment, the polymer resin may be a water-insoluble resin.

In one embodiment, as the mobile phase of the size exclusion chromatography in step (1), a non-polar solvent such as water, methanol, acetonitrile (AN), tetrahydrofuran (THF) or the like may be used. In other embodiments, the mobile phase is tetrahydrofuran (THF).

In one embodiment, in step (1), the size exclusion chromatography (SEC) automatically separates the polymer sample at 0.5 to 1 minute intervals, for example, at 0.7 minute intervals, in a 15 to 30 minute interval after the start of separation. .

In one embodiment, Ar or He is used as the carrier gas for pyrolysis in step (2) above.

In one embodiment, the pyrolysis in step (2) is carried out by raising the temperature from 100 to 800 ° C at a rate of 50 to 80 ° C / sec. For example, pyrolysis may be performed by heating at a rate of 100 ° C to 60 ° C / sec and maintaining it at 600 ° C for 60 seconds.

In one embodiment, the components separated out through size exclusion chromatography (SEC) in step (1) above are automatically captured in a vial and injected into a subsequent analyzer connected in series.

In addition, the present invention provides an analysis system used for qualitative and quantitative analysis of high molecular weight additives in polymer resins, including size exclusion chromatography, sample collection and automatic injectors, pyrolysis, and gas chromatography and mass spectrometry. do.

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical scope of the present invention. It is natural that such changes and modifications fall within the scope of the appended claims.

Example

1. Preparation of samples and standards

1.1 Pretreatment of standard products

-Chimasorb ^R 2020 standard was completely dissolved in tetrahydrofuran (THF) at concentrations of 1, 10, 20 and 40 mg / mL, respectively.

-Chimasorb ^R 119 standard and Cyasorb UV 3345 standard were completely dissolved in THF at a concentration of 10 mg / mL.

1.2 Sample preparation

2 g of freeze-crushed Nylon-6 resin was added to 10 mL of chloroform and shaken for 4 hours. After centrifuging the solution to precipitate the resin portion, the solution portion was fractionated. The aliquot was removed at room temperature through N ₂ purging. Subsequently, 1 mL of THF was added to completely dissolve and used as a sample solution. This sample contains Chimasorb ^R 2020 in an amount of 0.4% by weight.

2. SEC analysis conditions

It was analyzed using Shimadzu's Prominence HPLC system. For the column, Agilent's PLgel MIXED-B (length 300 mm, I.D. 7.5 mm, particle size: 10 μm) and PLgel MIXED-C (length 300 mm, I.D. 7.5 mm, particle size: 5 μm) were used. Tetrahydrofuran (tetrahydrofuran, HPLC) 100% was used as the mobile phase, the injection volume was adjusted to 50 μL, and the flow rate was adjusted to 1 mL / min. Six fractions were collected at 0.7 minute intervals in the 15.8 to 20.0 minute section after the start of separation.

3. Py-GC / MS analysis conditions

It was analyzed using GC / MS-QP2020 from Shimadzu. As a GC column, an RTX ™ -5MS column (length 30 m, I.D. 0.25 mm, thickness 0.25 μm, capillary) was used, and helium (He) was flowed at 1.0 mL / min as a carrier gas of the pyrolysis device. The oven temperature was maintained at 50 ° C. for 5 minutes, and then heated to 320 ° C. at 10 ° C. per minute and maintained for 10 minutes. The temperature condition of the pyrolyzer was increased from 100 ° C. (0 min) at a rate of 60 ° C. per second and maintained at 600 ° C. for 60 seconds. The solvent vent time was 300 seconds.

4. HALS-based high molecular weight additive database

LC-Py-GC / MS data of each standard product of Chimasorb ^R 2020, Chimasorb ^R 119 and Cyasorb ^R UV 3345 was obtained and database (D / B) was made. Chimasorb ^R 2020 has a molecular weight of 2600 to 3400 g / mol and confirmed characteristic m / z values of 58, 98, 124 and 140 (see FIG. 1). For reference, Chimasorb ^R 119 has a molecular weight of 2285.68 g / mol and characteristic m / z values of 58, 98, 124, 140, and 152 (see FIG. 3). Cyasorb ^R UV 3345 has a molecular weight of 1600 g / mol% and characteristic m / z values of 58, 98, 124, 138, 267, 279, and 336 (see FIG. 4).

Meanwhile, SEC and Py-GC / MS data for Chimasorb ^R 2020 are described in connection with Example 1 below.

Example 1: Chimasorb using SEC-Py-GC / MS continuously connected ^R  Qualitative analysis of 2020

As a sample, 0.4% by weight of Chimasorb ^R 2020 (molecular weight 2600 to 3400 g / mol), as described in "Pretreatment of 1.2 Sample" above, introduced pretreated Nylon-6 sample into SEC to separate Chimasorb ^R 2020 Then, the separated Chimasorb ^R 2020 was introduced into Py-GC / MS. From GC of Chimasorb ^R 2020, Chimasorb ^R in the same manner as that identified as 2020 standard, with a retention time (retention time) by the detecting the 28.2 min peak was analyzed by mass it. Characteristic peaks from residues containing piperidine in the mass spectrometry spectrum were identified at m / z 58, 98, 124 and 140.

The SEC data of the Chimasorb ^R 2020 standard and the sample are shown in Fig. 1A, and the total ion chromatogram (TIC) and mass spectrum of the gas generated in pyrolysis as Py-GC / MS data are shown in Figs. 1B and 1C, respectively. Did. In addition, the estimated structure of Chimasorb ^R 2020 based on the m / z value of the mass spectrum is shown in FIG. 2.

Example 2: Chimasorb ^R  Quantitative analysis of 2020

Simulate the mass value (m / z) in Py-GC / MS for fractions 3, 4 and 5 of SEC of Chimasorb ^R 2020 standard and Nylon-6 samples by concentration (1, 10, 20 and 40 mg / mL THF) selected ion monitoring). Linearity between concentration and peak area was confirmed for the Chimasorb ^R 2020 standard detected in fractions 3, 4 and 5 (R ² = 0.963).

Three characteristic peaks in Py-GC / MS for characteristic fraction 5 of SEC for both the Chimasorb ^R 2020 standard and Nylon-6 samples were confirmed to be m / z 140 at retention times of 24.1 minutes, 26.6 minutes and 28.2 minutes. Became. After confirming the correlation between the area and concentration of each detected peak and applying the Nylon-6 sample, the content of Chimasorb ^R 2020 in the sample was calculated, which was confirmed to be 0.49% by weight.

The Py-GC / MS SIM data and characteristic peak mass spectra of the Chimasorb ^R 2020 standard and Nylon-6 samples by concentration are shown in FIG. 5. In addition, the black line of the peak area (count) for the concentration of the Chimasorb ^R 2020 standard is shown in FIG. 6.

Comparative Example 1: Analysis of high molecular weight additive using MALDI-TOF MS

This comparative example, Example 1 in the same manner as Chimasorb ^R 2020 in a (molecular weight of 2600 to 3400g / mol) of Chimasorb ^R 2020 by using a MALDI-TOF MS according to the prior art intended for Nylon-6 sample containing 0.4 wt.% Qualitative analysis.

Two peaks ([M + H] ⁺ = 1062, 2425) at 1363 Da intervals were generated in the mass spectrometry spectrum obtained with MALDI-TOF MS for Nylon-6 samples, which could be estimated to correspond to Chimasorb ^R 2020. . The mass spectrum is shown in FIG. 7, and the structural formula of Chimasorb ^R 2020 detected at [M + H] ⁺ = 1062 and 2425 is as follows:

Comparative Example 2: Analysis of high molecular weight additive using 2D nuclear magnetic resonance spectroscopy (2D NMR spectroscopy)

In this comparative example, the same procedure as in Example 1 was performed on the Nylon-6 sample containing 0.4% by weight of Chimasorb ^R 2020 (molecular weight 2600 to 3400 g / mol), followed by pretreatment with a solvent extraction method according to the prior art and two-dimensional nuclear magnetic resonance spectroscopy. Chimasorb ^R 2020 was analyzed using.

In the ¹ H NMR spectrum and 2D ¹ H- ¹³ C HSQC (heteronuclear single quantum correlation) spectrum obtained for the Nylon-6 sample and the additive standard, peaks related to the high molecular weight additive in the polymer resin sample were not identified, and solvent extraction was applied. The presence of components, including additives in the solvent used, was confirmed. The ¹ H NMR spectrum and the 2D ¹ H- ¹³ C HSQC spectrum are shown in FIG. 8.

In this comparative example, it was impossible to secure qualitative and quantitative results, because the amount of the additive was less than 1% by weight and the peak assignment was difficult due to the mixture with the solvent used in the solvent extraction method. .

As can be seen from the above examples and comparative examples, quantitative analysis of high molecular weight additives in polymer samples by conventional MALDI-TOF MS and qualitative and quantitative analysis of high molecular weight additives in polymer samples by 2D NMR spectroscopy are difficult to obtain accurate results. . On the other hand, according to the present invention, a polymer resin containing a high molecular weight additive having a specific residue such as pyrimidine and morpholine is used as a low molecular weight compound using a continuously connected size exclusion chromatography-pyrolysis-gas chromatography / mass spectrometer. By decomposition, it was possible to confirm the structure of the high molecular weight additive and analyze its content.

As described above, specific parts of the present invention are described in detail through examples. For those skilled in the art, these specific techniques are only preferred embodiments, and the scope of the present invention is limited thereby. No, it will be obvious. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

1. As a method for analyzing a high molecular weight additive containing a piperidine or morpholine residue in a polymer resin sample,

   (1) separating a fraction corresponding to a high molecular weight additive by introducing the sample into size exclusion chromatography (SEC);

   (2) pyrolyzing the fraction of the separated high molecular weight additive by pyrolysis-gas chromatography / mass spectrometry (Py-GC / MS) to obtain a mass spectrometry spectrum for the pyrolized compound;

   (3) Qualitative by confirming the structure of the high molecular weight additive by comparing the m / z value of fragment peaks derived from piperidine or morpholine residues in the mass spectrometry spectrum with the m / z value of the standard foam. Analyzing; And

   (4) The analysis method including the step of adding the areas of the fragment peaks and quantitatively analyzing them by substituting them into a black line representing the peak area for the concentration of the standard foam.
2. The method of claim 1, wherein the molecular weight of the high molecular weight additive is 1,000 to 4,000 g / mol.
3. The method according to claim 1, wherein the high molecular weight additive is a hindered amine light stabilizer (HALS) selected from Chimasorb ^R 2020, Chimasorb ^R 119, Cyasorb ^R UV 3345 or mixtures thereof.
4. The method according to claim 3, wherein the hindered amine light stabilizer is Chimasorb ^R 2020.
5. The method according to claim 1, wherein the high molecular weight additive is Chimasorb ^R 2020, and its fragment peaks appear at m / z 58, 98, 124 and 140.
6.  The method of claim 1, wherein the high molecular weight additive is contained in an amount of 0.3 to 0.7% by weight based on the weight of the polymer resin.
7. The method of claim 1, wherein the polymer resin is a water-insoluble resin.
8. The analysis of claim 1, wherein in step (1), size exclusion chromatography (SEC) uses a solvent selected from the group consisting of water, methanol, acetonitrile (AN) and tetrahydrofuran (THF) as the mobile phase. Way.
9. The method of claim 1, wherein in step (1), size exclusion chromatography (SEC) automatically separates the polymer sample at intervals of 0.5 to 1 minute in a period of 15 to 30 minutes after separation starts.
10. The method according to claim 1, wherein the thermal decomposition in step (2) is performed by raising the temperature at a rate of 50 to 80 ° C / sec at 100 to 800 ° C.
11. 11. The method according to claim 10, wherein the thermal decomposition in step (2) is performed by raising the temperature from 100 ° C. to 60 ° C./sec at 600 ° C. for 60 seconds.
12. Size exclusion chromatography;

    Sample collection and automatic injector;

    Pyrolysis machine; And

    An analytical system used in the analytical method according to claim 1, comprising a gas chromatography / mass spectrometer.

Images