KR102153777B1 - Quantitative analysis method of trace amount of antistatic agent - Google Patents

Abstract

The present invention relates to a quantitative analysis method of an antistatic agent used for antistatic, for example, Atmer 163 (bis (2-hydroxyethyl) alkylamine) (bis (2-hydroxyethyl) alkylamine), including an antistatic agent In the supported catalyst manufacturing process, by analyzing the hexane filtrate by HPLC/MS with neat without dilution, the detection limit (LOD) can be lowered to analyze the presence and content of a trace amount of antistatic agent.

Description

Quantitative analysis method of trace amount of antistatic agent {QUANTITATIVE ANALYSIS METHOD OF TRACE AMOUNT OF ANTISTATIC AGENT}

The present invention relates to a method for quantitative analysis of a trace amount of antistatic agent, and more particularly, to a method for quantitatively analyzing a trace amount of an ethoxylated amine-based antistatic agent through a novel HPLC/MS analysis.

Static electricity causes various problems in the processing and use of various materials. Such static electricity can also cause product contamination because it collects dirt or dust that can damage product performance. Static electricity is a particular problem in the electronics industry because modern electronic devices are very sensitive to electrostatic discharge. In addition, in the case of dust lumps made by attaching dust by static electricity, quality deterioration in plastic molded products is caused.

A common means of preventing the formation or build-up of an electrostatic charge that causes static electricity is to use an antistatic agent. Antistatic agents are additives that are added to plastics (internal antistatic agent) or treated on the surface of a finished product (external antistatic agent) to reduce or eliminate static electricity formed on the surface of the product. In the case of using an internal antistatic agent, it is advantageous in terms of economy because an additional process for applying the antistatic agent after processing of the plastic molded product is not required.

의 내부 또는 외부 대전방지제로서, 정전기 전하의 증강을 감소시키고 LLDPE(linear low density polyethylene), HDPE(high density polyethylene), PP(polypropylene) 단독중합체 또는 공중합체와의 상용성이 좋다. 담지 촉매 제조 공정 중 헥산(hexane) 여액 내 Atmer 163의 함유 여부 및 그 함량은 가스 크로마토그래피(gas chromatography, GC)/질량분석(mass spectroscopy, MS) 또는 GC/불꽃이온화검출기(flame ionization detector, FID)로 분석하였다. 담지 촉매 제조 공정 중 사용되는 헥산은 촉매 제조 마지막 단계에 사용하는 용매이며 촉매 세척(washing)용으로 사용된다. 그런데, GC/MS 및 GC/FID의 경우 검출한계(limit of detection, LOD)가 높아서, 미량의 Atmer 163에 대한 정량분석이 어려웠다. 따라서, 시료 내 미량의 대전방지제에 대한 정량 분석법의 확립이 필요하다.Antistatic agent Atmer 163 is sometimes used to prevent static electricity.Atmer 163 (bis (2-hydroxyethyl) alkylamine) (bis (2-hydroxyethyl) alkylamine) is used in polyolefin, styrene, etc. Chemical formula

As an internal or external antistatic agent of, it reduces the build-up of electrostatic charge and has good compatibility with LLDPE (linear low density polyethylene), HDPE (high density polyethylene), and PP (polypropylene) homopolymer or copolymer. The content of Atmer 163 in the hexane filtrate during the supported catalyst manufacturing process and its content is determined by gas chromatography (GC)/mass spectroscopy (MS) or GC/flame ionization detector (FID). ) Was analyzed. Hexane used in the supported catalyst manufacturing process is a solvent used in the final step of preparing the catalyst and is used for washing the catalyst. However, in the case of GC/MS and GC/FID, the limit of detection (LOD) is high, making it difficult to quantitatively analyze a trace amount of Atmer 163. Therefore, it is necessary to establish a quantitative analysis method for a trace amount of antistatic agent in a sample.

The present inventors have developed a method for analyzing the content and whether a trace amount of Atmer 163 is contained through novel HPLC/MS analysis. According to the analysis method of the present invention, the LOD is very low compared to the conventional analysis method, so that even if Atmer 163 is present in a trace amount, quantitative analysis is possible.

It is an object of the present invention to provide an analysis method for the content and the presence of an antistatic agent, for example Atmer 163.

In order to achieve the above object, the present invention provides a method of HPLC/MS analysis of a hexane filtrate including an antistatic agent in a supported catalyst manufacturing process.

In the method of the present invention, a standard solution containing an antistatic agent diluted with acetone is analyzed by HPLC/MS, and a hexane filtrate containing an antistatic agent in the supported catalyst manufacturing process is analyzed by HPLC/MS with neat, and then the Calculate the peak area on the HPLC/MS chromatogram of the standard solution, calculate the peak area in the same manner for the hexane filtrate, and then substitute it for each calibration curve to calculate the concentration of the antistatic agent in the sample. have.

In one embodiment, the peak may be extracted with m/z=288 and m/z=316.

In one embodiment, the concentration of the antistatic agent in the sample can be calculated from the calibration curve according to the following equation:

Content of antistatic agent (ppm, μg/ml) = C _cal (here, C _cal is the concentration obtained by substituting the area of the peak detected in the calibration curve).

In one embodiment, the type of HPLC/MS is not particularly limited as long as it is commonly used in the art, and for example, Waters Alliance 2695 and Waters 3100 mass detector of Waters may be used. .

In one embodiment, the antistatic agent may be an ethoxylated amine-based antistatic agent.

In one embodiment, the antistatic agent may include a bis(2-hydroxyethyl)alkylamine antistatic agent.

In one embodiment, the antistatic agent may be Atmer 163.

In one embodiment, the concentration of Atmer 163 in the sample is the above-described Atmer as an extracted peak with m/z=288 (R=C ₁₃ ) and m/z=316 (R=C ₁₅ ) in HPLC/MS. Based on the formula of 163, it is possible to perform quantitative analysis and whether Atmer 163 of R=C ₁₃ and Atmer 163 of R=C ₁₅ each contain.

According to the quantitative analysis method of the present invention, by HPLC/MS analysis of the hexane filtrate containing the antistatic agent in the process of manufacturing the supported catalyst with neat, the detection limit (LOD) is lowered to analyze the presence and content of a trace amount of the antistatic agent. can do.

1 shows an HPLC/MS chromatogram of an Atmer 163 standard solution according to an embodiment of the present invention.
Figure 2 shows a calibration curve (B) of Atmer 163 (R = C ₁₃₎ calibration curve (calibration curve) (A) and Atmer 163 (R = C ₁₅₎ in accordance with one embodiment of the present invention.
3 is an LC/MS extracted ion chromatogram of Atmer 163 (R=C ₁₃ ) standard solution and sample according to an embodiment of the present invention and LC of Atmer 163 (R=C ₁₅ ) standard solution and sample. /MS It shows the extracted ion chromatogram (B).

Hereinafter, an aspect of the present invention will be described in more detail.

Terms and words used in this specification and claims should not be construed as being limited to their usual or dictionary meanings, and that the inventor can appropriately define the concept of terms in order to describe his own invention in the best way. Based on the principle, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

The present invention is a method for analyzing the presence and content of an antistatic agent, for example, Atmer 163, which has been difficult to quantitatively analyze when the detection limit (LOD) is high in the case of conventional GC/MS or GC/FID analysis. It aims to provide.

In order to achieve the above object, the present invention provides a method for qualitative and quantitative analysis of a hexane filtrate including an antistatic agent in a process for preparing a supported catalyst by HPLC/MS with neat.

In the present invention, the content and content of an antistatic agent, for example, Atmer 163, in the hexane filtrate during the supported catalyst preparation process was analyzed by HPLC/MS using a neat sample of the hexane filtrate. As the concentration of Atmer 163 in the sample is low, the peaks extracted with m/z = 288 (R = C ₁₃ ) and m / z = 316 (R = C ₁₅ ) in HPLC/MS are expressed in the above formula of Atmer 163. Based on this, it was possible to perform quantitative analysis and whether each of Atmer 163 of R=C ₁₃ and Atmer 163 of R=C ₁₅ were contained. As a result of the analysis, it was confirmed that Atmer 163 in the sample was a mixture of the structure of R=C _{13 and} the structure of R=C ₁₅ . In the conventional GC/FID analysis, the LOD of Atmer 163 was 500 ppm, while the LOD of Atmer 163 was lowered to 0.1 ppm during the HPLC/MS analysis of the present invention, enabling trace analysis.

In one embodiment, HPLC/MS analysis of an antistatic standard solution diluted with acetone, and HPLC/MS analysis of a hexane filtrate containing an antistatic agent during the supported catalyst preparation process with neat, and then HPLC/MS analysis of the standard solution After calculating the peak area on the chromatogram and calculating the peak area in the same manner for the hexane filtrate, the concentration of the antistatic agent in the sample can be calculated by substituting it into each calibration curve.

In one embodiment, the peak may be extracted with m/z=288 and m/z=316.

In one embodiment, the concentration of the antistatic agent in the sample can be calculated from the calibration curve according to the following equation:

Content of antistatic agent (ppm, μg/ml) = C _cal (here, C _cal is the concentration obtained by substituting the area of the peak detected in the calibration curve).

In one embodiment, the type of HPLC/MS is not particularly limited as long as it is commonly used in the art, and for example, Waters Alliance 2695 and Waters 3100 mass detector of Waters may be used. .

In one embodiment, the antistatic agent may be an ethoxylated amine-based antistatic agent.

In one embodiment, the antistatic agent may include a bis(2-hydroxyethyl)alkylamine antistatic agent.

In one embodiment, the antistatic agent may be Atmer 163.

In one embodiment, the concentration of Atmer 163 in the sample is the above-described Atmer as an extracted peak with m/z=288 (R=C ₁₃ ) and m/z=316 (R=C ₁₅ ) in HPLC/MS. Based on the formula of 163, it is possible to perform quantitative analysis and whether Atmer 163 of R=C ₁₃ and Atmer 163 of R=C ₁₅ each contain.

Hereinafter, the present invention will be described in more detail through examples. The examples described below are only for describing the present invention in more detail, and it is for those of ordinary skill in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. It will be self-evident.

<Example>

Below, the sample used in the qualitative and quantitative analysis method of the present invention, HPLC/MS analysis conditions, and calculation of the content of the antistatic agent in the sample are described.

1. Analysis purpose

It is intended to check the content and whether Atmer 163 is contained as an antistatic agent in the hexane filtrate during the process.

2. Sample preparation

1) Preparation of standard solution: Put about 25mg of Atmer 163 standard into a 25mL volumetric flask and measure the weight (accurately to 0.1mg), then use 1/2, 1/10, 1 with acetone. After preparing diluted solutions of /20, 1/100, 1/200, and 1/1000, these solutions were analyzed by HPLC/MS.

2) Sample solution preparation : During the supported catalyst preparation process, the hexane filtrate containing Atmer 163 was analyzed by HPLC/MS with neat without diluting with acetone.

3. HPLC/MS analysis conditions

Waters Alliance 2695 and Waters 3100 mass detectors from Waters were used for the analysis.

Column Capcellpak C ₁₈ was used. Mobile phase was prepared by adding 0.1% of trifluoroacetic acid (TFA), Aldrich) to acetonitrile (CAN), for HPLC, JT Baker) and ultrapure water (MILLIPORE, Milli-Q, specific resistance 18㏁). I did. Mobile phases A and B were analyzed under gradient conditions for 35 minutes to obtain chromatograms. Detailed analysis conditions are as follows.

-Column: Capcellpak C ₁₈ , Shiseido (4.6mm ID × 50mm L., 3㎛)

-Eluent: A; ACN + 0.1% TFA=100%

B; H ₂ O + 0.1% TFA=100%

-Flow rate: 1.0 mL/min

-Column temperature: 40℃

-Injection volume: 10µl

-Equilibrium time: 5 minutes

4. Standard solution chromatogram

Atmer 163 is a mixture structure of R=C ₁₃ structure and R=C ₁₅ structure, and the retention time was 15.3 minutes for Atmer 163 (R=C ₁₃ ) and 17.0 minutes for Atmer 163 (R=C ₁₅ ).

Since the concentration of the additive Atmer 163 in the sample is low, the peaks extracted with m/z=288 (R=C ₁₃ ) and m/z=316 (R=C ₁₅ ) in HPLC/MS are used for qualitative and quantitative analysis of each component . The HPLC/MS chromatogram of the standard solution is shown in Figure 1.

5. Calculation of Atmer 163 content

For the analyzed standard solution, m/z=288 and m/z=316 peaks extracted on the HPLC/MS chromatogram were confirmed, and the area of the peak was calculated. A calibration curve was drawn with the standard solution concentration and the calculated peak area. At this time, the correlation coefficient (R ² ) should be 0.995 or higher. For the sample solution, check the extracted m/z=288 and m/z=316 peaks of Atmer 163 on the chromatogram, calculate the area of the peak, and substitute it into each calibration curve to determine the concentration of Atmer 163 in the sample by the following formula: It was calculated according to:

Atmer 163 content (ppm, μg/ml) = C _cal

In the above equation, C _cal is the concentration obtained by substituting the area of the peak detected in the calibration curve.

The calibration curve of Atmer 163 (R=C ₁₃ ) and the calibration curve of Atmer 163 (R=C ₁₅ ) are shown in FIG. 2 as (A) and (B), respectively.

6. Analysis result

The results calculated using each calibration curve of Atmer 163 (R=C ₁₃ , R=C ₁₅ ) are as follows (Atmer 163 LOD: 0.1ppm)

LC/MS extracted ion chromatogram of Atmer 163 (R=C ₁₃ ) standard solution and sample and LC/MS extracted ion chromatogram of Atmer 163 (R=C ₁₅ ) standard solution and sample are shown in FIG. ) And (B).

Looking at the basis of FIG. 3, the retention times of samples Atmer 163 (R=C ₁₃ ) and Atmer 163 (R=C ₁₅ ) are approximately the same as the LC/MS extracted ion chromatogram for the standard solution, respectively, 15.3 minutes and It can be seen that it is 17.0 minutes. Therefore, according to the analysis method of the present invention, it is possible to accurately analyze the presence and content of Atmer 163 in the hexane filtrate including the antistatic agent during the supported catalyst manufacturing process.

In the above, a preferred embodiment according to the present invention has been described, but this is exemplary, and the scope of the present invention is not limited thereby, and various modifications and other equivalent embodiments are possible. You can understand that it does. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (6)

Including analyzing the hexane filtrate by HPLC/MS in the process of preparing a supported catalyst including a bis(2-hydroxyethyl)alkylamine) antistatic agent,
The HPLC/MS analysis conditions are as follows, the method of analyzing the content of the antistatic agent:
Eluent: A; ACN + 0.1% TFA=100%
B; H ₂ O + 0.1% TFA=100%

Flow rate: 1 mL/min
ES cone: 50V
Capillary voltage: 3kV. The method of claim 1, wherein the standard solution containing the antistatic agent diluted with acetone was analyzed by HPLC/MS, and the hexane filtrate containing the antistatic agent during the supported catalyst preparation process was analyzed by HPLC/MS with neat. Next, the peak area was calculated on the HPLC/MS chromatogram of the standard solution, and the peak area was calculated for the hexane filtrate, and then the concentration of the antistatic agent in the sample was calculated by substituting it for each calibration curve. Analysis method comprising that. The method of claim 2, wherein the peak of the hexane filtrate is extracted with m/z=288 and m/z=316. The method of claim 1, wherein the antistatic agent has the formula

Atmer 163 of that, the analysis method. The method of claim 4, wherein the Atmer 163 is a structure of a mixture of R=C ₁₃ structure and R=C ₁₅ structure. The method of claim 1, wherein the content of the antistatic agent is calculated according to the following equation:
Content of antistatic agent (ppm, μg/ml) = C _cal
In the above equation, C _cal is the concentration obtained by substituting the area of the peak detected in the calibration curve.

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