KR20190029004A - Quantitative analysis method of trace amount of antistatic agent - Google Patents

Quantitative analysis method of trace amount of antistatic agent Download PDF

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KR20190029004A
KR20190029004A KR1020170116014A KR20170116014A KR20190029004A KR 20190029004 A KR20190029004 A KR 20190029004A KR 1020170116014 A KR1020170116014 A KR 1020170116014A KR 20170116014 A KR20170116014 A KR 20170116014A KR 20190029004 A KR20190029004 A KR 20190029004A
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antistatic agent
atmer
hplc
content
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KR102153777B1 (en
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남문자
김병현
진미경
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주식회사 엘지화학
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N30/02—Column chromatography
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Abstract

The present invention relates to a method for quantitative analysis of an antistatic agent, for example, Atmer 163 (bis(2-hydroxyethyl)alkylamine) used for preventing static electricity. The presence and the content of the antistatic agent in a trace amount can be analyzed by lowering the detection limit (LOD) by analyzing a non-diluted hexane filtrate with neat, thereby performing HPLC/MS analysis in a process for manufacturing a supported catalyst including the antistatic agent.

Description

미량의 대전방지제의 정량분석방법 {QUANTITATIVE ANALYSIS METHOD OF TRACE AMOUNT OF ANTISTATIC AGENT}TECHNICAL FIELD [0001] The present invention relates to a method for quantitatively analyzing an antistatic agent,

본 발명은 미량의 대전방지제의 정량분석방법에 관한 것으로, 더욱 상세하게는 미량의 에톡실화 아민(ethoxylated amine)계 대전방지제를 신규한 HPLC/MS 분석을 통해 정량분석하는 방법에 관한 것이다.More particularly, the present invention relates to a method for quantitatively analyzing a small amount of an ethoxylated amine-based antistatic agent through a novel HPLC / MS analysis.

정전기는 각종 물질의 가공이나 사용에 있어서 여러 가지 문제를 일으키는 원인이 된다. 이러한 정전기는 제품 성능에 손상을 줄 수 있는 오물 또는 먼지를 모으기 때문에 제품의 오염을 야기시키기도 한다. 정전기는 전자 산업에 있어서 특히 문제인데, 현대식 전자 장치가 정전기 방전에 매우 예민하기 때문이다. 또한, 정전기에 의해 먼지가 부착되어 만들어지는 먼지 덩어리의 경우 플라스틱 성형품에서 품질 저하를 야기한다. Static electricity causes various problems in the processing and use of various materials. Such static electricity can also cause contamination of the product because it collects dirt or dust that can damage product performance. Static electricity is particularly problematic in the electronics industry because modern electronic devices are very sensitive to electrostatic discharge. Further, in the case of a dust lump formed by attaching dust by static electricity, the quality of the plastic molded article is deteriorated.

정전기를 일으키는 정전기 전하의 형성 내지 증강을 방지하는 통상의 수단은 대전방지제를 사용하는 것이다. 대전방지제란 플라스틱 등에 첨가(내부 대전방지제)되거나 완성된 제품의 표면에 처리(외부 대전방지제)하여 해당 제품의 표면에 형성되는 정전기를 감소시키거나 제거하는 작용을 하는 첨가제를 말한다. 내부 대전방지제를 사용하는 경우 플라스틱 성형품의 가공 후 대전방지제를 도포하기 위한 추가의 공정이 필요하지 않기 때문에 경제적인 측면에서 유리하다.An ordinary means for preventing the formation or enhancement of the electrostatic charge causing static electricity is to use an antistatic agent. An antistatic agent is an additive that acts to add or remove static electricity on the surface of a finished product by adding (external antistatic agent) to the finished product surface (external antistatic agent). When an internal antistatic agent is used, an additional step of applying an antistatic agent after processing of the plastic molded article is not necessary, which is advantageous from the economical point of view.

정전기 방지용으로 대전방지제 Atmer 163이 사용되는 경우가 있는데, Atmer 163(비스(2-하이드록시에틸)알킬아민)(bis(2-hydroxyethyl)alkylamine)은 폴리올레핀(polyolefin), 스티렌(styrene) 등에 사용되는 화학식

Figure pat00001
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.Atmer 163 (bis (2-hydroxyethyl) alkylamine) bis (2-hydroxyethyl) alkylamine) is used for polyolefin, styrene and the like in antistatic The
Figure pat00001
(LLDPE), HDPE (high density polyethylene), and polypropylene (PP) homopolymers or copolymers as the antistatic agent. The content and content of Atmer 163 in a hexane filtrate in a supported catalyst production process can be measured by gas chromatography (GC) / mass spectroscopy (MS) or GC / flame ionization detector (FID ). The hexane used in the supported catalyst preparation process is the solvent used in the final stage of the catalyst preparation and is used for washing the catalyst. However, GC / MS and GC / FID have a high limit of detection (LOD), making quantitative analysis of trace amounts of Atmer 163 difficult. Therefore, it is necessary to establish a quantitative analysis method for a small amount of antistatic agent in the sample.

본 발명자들은 미량의 Atmer 163을 신규한 HPLC/MS 분석을 통해 함유 여부 및 그 함량을 분석하는 방법을 개발하였다. 본 발명의 분석방법에 따르면 LOD가 기존의 분석방법에 비해 매우 낮아져 Atmer 163이 미량으로 존재하여도 정량분석이 가능하다.The present inventors have developed a method for analyzing the content and the content of Atmer 163 through a novel HPLC / MS analysis. According to the analysis method of the present invention, the LOD is much lower than that of the conventional analysis method, so that quantitative analysis is possible even when a small amount of Atmer 163 exists.

본 발명의 목적은 대전방지제, 예를 들어, Atmer 163의 함유 여부 및 함량의 분석법을 제공하는 것이다.It is an object of the present invention to provide an assay for the content and content of an antistatic agent, for example, Atmer 163.

상기와 같은 목적을 달성하기 위하여, 본 발명에서는 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액을 HPLC/MS 분석하는 방법을 제공한다.In order to achieve the above object, the present invention provides a method for HPLC / MS analysis of a hexane filtrate containing an antistatic agent during a supported catalyst production process.

본 발명의 방법에서는 아세톤(acetone)으로 희석한 대전방지제 함유 표준 용액을 HPLC/MS로 분석하고 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액을 니트(neat)로 HPLC/MS로 분석한 다음, 상기 표준 용액의 HPLC/MS 크로마토그램(chromatogram) 상에서 피크 면적을 계산하고 상기 헥산 여액에 대해 마찬가지로 피크 면적을 계산한 다음, 각각의 검정 곡선(calibration curve)에 대입하여 시료 내 대전방지제의 농도를 계산할 수 있다. In the method of the present invention, the standard solution containing the antistatic agent diluted with acetone is analyzed by HPLC / MS, the hexane filtrate containing the antistatic agent during the supported catalyst production process is analyzed by HPLC / MS with neat, The peak area is calculated on the HPLC / MS chromatogram of the standard solution and the peak area is similarly calculated for the hexane filtrate, and the concentration of the antistatic agent in the sample can be calculated by assigning to each calibration curve have.

한 실시양태에서, 상기 피크는 m/z=288 및 m/z=316으로 추출된 것일 수 있다.In one embodiment, the peak may be extracted with m / z = 288 and m / z = 316.

한 실시양태에서, 상기 검정 곡선으로부터 시료 내 대전방지제의 농도를 아래 식에 따라 계산할 수 있다:In one embodiment, the concentration of the antistatic agent in the sample from the calibration curve can be calculated according to the following equation:

대전방지제의 함량(ppm, μg/ml) = Ccal (여기서, Ccal은 검량 곡선에서 검출된 피크의 면적을 대입하여 구한 농도이다).(Ppm, μg / ml) = C cal (where C cal is the concentration obtained by substituting the area of the peak detected in the calibration curve).

한 실시양태에서, 상기 HPLC/MS의 종류는 당업계에서 통상적으로 사용되는 것이면 특별히 한정되지 않고, 예를 들어, 워터스(Waters)사의 Waters Alliance 2695와 Waters 3100 질량 검출기(mass detector)를 사용할 수 있다.In one embodiment, the type of HPLC / MS is not particularly limited as long as it is commonly used in the art. For example, a Waters Alliance 2695 from Waters and a Waters 3100 mass detector can be used .

한 실시양태에서, 상기 대전방지제는 에톡실화 아민계 대전방지제일 수 있다.In one embodiment, the antistatic agent may be an ethoxylated amine antistatic agent.

한 실시양태에서, 상기 대전방지제는 비스(2-하이드록시에틸)알킬아민 대전방지제를 포함할 수 있다.In one embodiment, the antistatic agent may comprise a bis (2-hydroxyethyl) alkylamine antistatic agent.

한 실시양태에서, 상기 대전방지제는 Atmer 163일 수 있다.In one embodiment, the antistatic agent may be Atmer 163.

한 실시양태에서, 시료 내 Atmer 163의 농도는 HPLC/MS에서 m/z=288(R=C13)과 m/z=316(R=C15)로 추출된(extracted) 피크로 상기한 Atmer 163의 화학식에 근거해 R=C13의 Atmer 163과 R=C15의 Atmer 163 각각의 함유 여부 및 정량분석을 할 수 있다.In one embodiment, the sample concentration of Atmer 163 is a HPLC / MS at m / z = 288 (R = C 13) and m / z = 316 (R = C 15) by the in the extract (extracted) peak with Atmer Based on the formula of 163, it is possible to determine the content and quantitative analysis of Atmer 163 of R = C 13 and Atmer 163 of R = C 15 .

본 발명의 정량분석방법에 따르면, 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액을 니트(neat)로 HPLC/MS 분석함으로써, 검출 한계(LOD)를 낮춰 미량의 대전방지제의 함유 여부 및 함량을 분석할 수 있다.According to the quantitative analysis method of the present invention, the detection limit (LOD) is lowered by HPLC / MS analysis of a hexane filtrate containing an antistatic agent during a supported catalyst production process with a neat to analyze the content and content of a small amount of an antistatic agent can do.

도 1은 본 발명의 한 실시양태에 따른 Atmer 163 표준 용액의 HPLC/MS 크로마토그램을 나타낸 것이다.
도 2는 본 발명의 한 실시양태에 따른 Atmer 163(R=C13)의 검량 곡선(calibration curve)(A) 및 Atmer 163(R=C15)의 검량 곡선(B)을 나타낸 것이다.
도 3은 본 발명의 한 실시양태에 따른 Atmer 163(R=C13) 표준 용액 및 시료의 LC/MS 추출된 이온 크로마토그램(A)과 Atmer 163(R=C15) 표준 용액 및 시료의 LC/MS 추출된 이온 크로마토그램(B)을 나타낸 것이다.Figure 1 depicts an HPLC / MS chromatogram of an Atmer 163 standard solution according to one 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 Atmer according to one embodiment of the present invention 163 (R = C 13) standard solution and LC / MS extracted ion chromatogram (A) and Atmer 163 of the sample (R = C 15) of the standard solution and the sample LC / MS extracted ion chromatogram (B).

이하에서는, 본 발명의 양태를 보다 구체적으로 설명하기로 한다.Hereinafter, embodiments of the present invention will be described in more detail.

본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 안되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor can properly define the concept of the term to describe its invention in the best possible way And should be construed in accordance with the principles and meanings and concepts consistent with the technical idea of the present invention.

본 발명은 기존의 GC/MS 또는 GC/FID 분석의 경우 검출 한계(LOD)가 높아 미량으로 존재하는 경우에 정량분석이 어려웠던 대전방지제, 예를 들어, Atmer 163의 함유 여부 및 함량을 분석하는 방법을 제공하는 것을 목적으로 한다. The present invention relates to a method for analyzing the content and content of an antistatic agent, for example, Atmer 163, which was difficult to quantitatively analyze in the case of a trace amount (LOD) due to high GC / MS or GC / FID analysis And to provide the above objects.

상기 목적을 달성하기 위해, 본 발명은 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액을 니트(neat)로 HPLC/MS로 정성 및 정량분석하는 방법을 제공한다.In order to achieve the above object, the present invention provides a method for qualitatively and quantitatively analyzing a hexane filtrate containing an antistatic agent in a supported catalyst production process with neat by HPLC / MS.

본 발명에서는 담지 촉매 제조 공정 중 헥산 여액 내 대전방지제, 예를 들어, Atmer 163의 함유 여부 및 함량을 헥산 여액 니트(neat) 시료를 이용하여 HPLC/MS로 분석하였다. 시료 내 Atmer 163의 농도가 낮아서 HPLC/MS에서 m/z=288(R=C13)과 m/z=316(R=C15)로 추출된(extracted) 피크로 상기한 Atmer 163의 화학식에 근거해 R=C13의 Atmer 163과 R=C15의 Atmer 163 각각의 함유 여부 및 정량분석을 할 수 있었다. 분석 결과, 시료 내 Atmer 163은 R=C13의 구조와 R=C15의 구조의 혼합물 형태임을 확인하였다. 기존 GC/FID 분석 시 Atmer 163의 LOD가 500ppm인 반면, 본 발명의 HPLC/MS 분석 시 Atmer 163의 LOD가 0.1ppm으로 낮아져 미량 분석이 가능하게 된 것이다.In the present invention, the presence and content of an antistatic agent, for example, Atmer 163, in a hexane filtrate in a supported catalyst production process was analyzed by HPLC / MS using a hexane filtrate neat sample. The concentration of Atmer 163 in the sample was low and the peak of the extracted Atmer 163 peak at m / z = 288 (R = C 13 ) and m / z = 316 (R = C 15 ) Based on the results, it was possible to determine the content and quantitative analysis of Atmer 163 of R = C 13 and Atmer 163 of R = C 15 . As a result of analysis, Atmer 163 in the sample was confirmed to be 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, whereas the LOD of Atmer 163 was lowered to 0.1 ppm in the HPLC / MS analysis of the present invention, enabling trace analysis.

한 실시양태에서, 아세톤으로 희석한 대전방지제 표준 용액을 HPLC/MS 분석하고 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액을 니트(neat)로 HPLC/MS 분석한 다음, 상기 표준 용액의 HPLC/MS 크로마토그램 상에서 피크 면적을 계산하고 상기 헥산 여액에 대해 마찬가지로 피크 면적을 계산한 다음, 각각의 검정 곡선에 대입하여 시료 내 대전방지제의 농도를 계산할 수 있다.In one embodiment, an antistatic agent standard solution diluted with acetone was subjected to HPLC / MS analysis, and a hexane filtrate containing an antistatic agent during a supported catalyst production process was subjected to HPLC / MS analysis using neat, and then the HPLC / MS The peak area on the chromatogram is calculated and the peak area is similarly calculated for the hexane filtrate, and then the value is substituted into each calibration curve to calculate the concentration of the antistatic agent in the sample.

한 실시양태에서, 상기 피크는 m/z=288 및 m/z=316으로 추출된 것일 수 있다.In one embodiment, the peak may be extracted with m / z = 288 and m / z = 316.

한 실시양태에서, 상기 검정 곡선으로부터 시료 내 대전방지제의 농도를 아래 식에 따라 계산할 수 있다:In one embodiment, the concentration of the antistatic agent in the sample from the calibration curve can be calculated according to the following equation:

대전방지제의 함량(ppm, μg/ml) = Ccal (여기서, Ccal 은 검량 곡선에서 검출된 피크의 면적을 대입하여 구한 농도이다).(Ppm, μg / ml) = C cal (where C cal is the concentration obtained by substituting the area of the peak detected in the calibration curve).

한 실시양태에서, 상기 HPLC/MS의 종류는 당업계에서 통상적으로 사용되는 것이면 특별히 한정되지 않고, 예를 들어, 워터스(Waters)사의 Waters Alliance 2695와 Waters 3100 질량 검출기(mass detector)를 사용할 수 있다.In one embodiment, the type of HPLC / MS is not particularly limited as long as it is commonly used in the art. For example, a Waters Alliance 2695 from Waters and a Waters 3100 mass detector can be used .

한 실시양태에서, 상기 대전방지제는 에톡실화 아민계 대전방지제일 수 있다.In one embodiment, the antistatic agent may be an ethoxylated amine antistatic agent.

한 실시양태에서, 상기 대전방지제는 비스(2-하이드록시에틸)알킬아민 대전방지제를 포함할 수 있다.In one embodiment, the antistatic agent may comprise a bis (2-hydroxyethyl) alkylamine antistatic agent.

한 실시양태에서, 상기 대전방지제는 Atmer 163일 수 있다.In one embodiment, the antistatic agent may be Atmer 163.

한 실시양태에서, 시료 내 Atmer 163의 농도는 HPLC/MS에서 m/z=288(R=C13)과 m/z=316(R=C15)로 추출된(extracted) 피크로 상기한 Atmer 163의 화학식에 근거해 R=C13의 Atmer 163과 R=C15의 Atmer 163 각각의 함유 여부 및 정량분석을 할 수 있다. In one embodiment, the sample concentration of Atmer 163 is a HPLC / MS at m / z = 288 (R = C 13) and m / z = 316 (R = C 15) by the in the extract (extracted) peak with Atmer Based on the formula of 163, it is possible to determine the content and quantitative analysis of Atmer 163 of R = C 13 and Atmer 163 of R = C 15 .

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 아래에 기재한 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 당업계에서 통상의 지식을 가진 자에 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention, It will be self-evident.

<실시예><Examples>

아래에 본 발명의 정성 및 정량 분석방법에 사용되는 시료, HPLC/MS 분석조건 및 시료 내 대전방지제의 함량 계산에 대해 기재한다.Hereinafter, the samples used in the qualitative and quantitative analysis methods of the present invention, the HPLC / MS analysis conditions, and the contents of the antistatic agent in the sample will be described.

1. 분석 목적 1. Purpose of Analysis

공정 중 헥산 여액 내 대전방지제로서의 Atmer 163의 함유 여부 및 함량을 확인하고자 하는 것이다.The presence and content of Atmer 163 as an antistatic agent in the hexane filtrate during the process is checked.

2. 시료 준비 2. Sample Preparation

1) 표준 용액 제조: 25mL 들이 볼루메트릭 플라스크(volumetric flask)에 약 25mg의 Atmer 163 표준품을 넣고 무게를 측정한 후(0.1mg까지 정확히 측정), 아세톤을 사용하여 1/2, 1/10, 1/20, 1/100, 1/200, 1/1000의 희석 용액을 만든 후 이 용액들을 HPLC/MS로 분석하였다.1) Preparation of standard solution: About 25 mg of Atmer 163 standard was weighed in a 25-mL volumetric flask, weighed (accurately measured to 0.1 mg), and 1/2, 1/10, 1 / 20, 1/100, 1/200, 1/1000 diluted solutions were prepared and analyzed by HPLC / MS.

2) 시료 용액 제조: 담지 촉매 제조 공정 중 Atmer 163을 포함한 헥산 여액을 아세톤으로 희석하지 않고 니트(neat)로 HPLC/MS로 분석하였다.2) Preparation of sample solution : The hexane filtrate containing Atmer 163 in the supported catalyst production process was analyzed by HPLC / MS with neat without diluting with acetone.

3. HPLC/MS 분석조건 3. HPLC / MS analysis conditions

워터스(Waters)사의 Waters Alliance 2695와 Waters 3100 질량 검출기(mass detector)를 분석에 사용하였다. A Waters Alliance 2695 from Waters and a Waters 3100 mass detector were used for the analysis.

컬럼은 Capcellpak C18을 사용하였다. 이동상은 아세토니트릴(acetonitrile(CAN), HPLC용, J.T. Baker)과 초순수(MILLIPORE사, Milli-Q, 비저항18㏁)에 트리플루오로아세트산(trifluoroacetic acid(TFA), Aldrich)을 0.1% 첨가하여 제조하였다. 이동상 A 및 B를 구배 조건으로 35분 동안 분석하여 크로마토그램을 얻었다. 자세한 분석 조건은 다음과 같다.The column was Capcellpak C 18 . The mobile phase was prepared by adding 0.1% trifluoroacetic acid (TFA) (Aldrich) to acetonitrile (CAN), HPLC, JT Baker) and ultrapure water (Millipore, Milli-Q, Respectively. Mobile phase A and B were analyzed for 35 minutes under gradient conditions to obtain a chromatogram. Detailed analysis conditions are as follows.

- 컬럼: Capcellpak C18, Shiseido (4.6mm I.D. × 50mm L., 3㎛)- Column: Capcellpak C 18 , Shiseido (4.6 mm ID x 50 mm L., 3 m)

- 용리액(eluent): A; ACN + 0.1% TFA=100% - eluent: A; ACN + 0.1% TFA = 100%

B; H2O + 0.1% TFA=100%B; H 2 O + 0.1% TFA = 100%

Figure pat00002
Figure pat00002

- 유속(flow rate): 1.0mL/분- Flow rate: 1.0 mL / min

- 컬럼 온도(column temperature): 40℃- column temperature: 40 DEG C

- 유입 용량(injection volume): 10㎕- Injection volume (injection volume): 10 μl

- 평형 시간(equlibrium time): 5분 - equlibrium time: 5 minutes

Figure pat00003
Figure pat00003

4. 표준 용액 크로마토그램 4. Standard Solution Chromatogram

Atmer 163은 R=C13 구조와 R=C15 구조의 혼합물 구조이며, 머무름 시간은 Atmer 163(R=C13)은 15.3분이고, Atmer 163(R=C15)은 17.0분이었다.Atmer 163 has a mixture structure of R = C 13 structure and R = C 15 structure. The retention time is 15.3 minutes for Atmer 163 (R = C 13 ) and 17.0 minutes for Atmer 163 (R = C 15 ).

시료 내 첨가제 Atmer 163의 농도가 낮아 HPLC/MS에서 m/z=288(R=C13)과 m/z=316(R=C15)로 추출된 피크로 각 성분의 정성 및 정량 분석을 한다. 표준 용액의 HPLC/MS 크로마토그램을 도 1에 나타냈다.The concentration of Atmer 163 in the sample is low and the qualitative and quantitative analysis of each component is carried out with a peak extracted at m / z = 288 (R = C 13 ) and m / z = 316 (R = C 15 ) . HPLC / MS chromatogram of the standard solution is shown in Fig.

5. Atmer 163 함량의 계산 5. Calculation of Atmer 163 content

분석된 표준 용액에 대해 HPLC/MS 크로마토그램 상에서 추출된 m/z=288 및 m/z=316 피크를 확인하고 피크의 면적을 계산하였다. 표준 용액 농도와 계산된 피크 면적으로 검량 곡선을 그렸다. 이 때 상관계수(correlation coefficient; R2)는 0.995 이상이어야 한다. 시료 용액에 대해 크로마토그램 상에서 Atmer 163의 추출된 m/z=288 및 m/z=316 피크를 확인하고 피크의 면적을 계산한 후 각각의 검량 곡선에 대입하여 시료 내 Atmer 163의 농도를 아래 식에 따라 계산하였다: The m / z = 288 and m / z = 316 peaks extracted on the HPLC / MS chromatogram for the analyzed standards were determined and the area of the peaks was calculated. A calibration curve was drawn with the concentration of the standard and the calculated peak area. The correlation coefficient (R 2 ) should be not less than 0.995. For the sample solution, the extracted m / z = 288 and m / z = 316 peaks of Atmer 163 were identified on the chromatogram, and the area of the peak was calculated and substituted for each calibration curve to determine the concentration of Atmer 163 in the sample according to the following equation Lt; / RTI &gt;

Atmer 163의 함량(ppm, μg/ml) = Ccal Content of Atmer 163 (ppm, μg / ml) = C cal

위의 식에서, Ccal은 검량 곡선에서 검출된 피크의 면적을 대입하여 구한 농도이다.In the above equation, C cal is the concentration obtained by substituting the area of the peak detected in the calibration curve.

Atmer 163(R=C13)의 검량 곡선 및 Atmer 163(R=C15)의 검량 곡선을 도 2에 각각 (A) 및 (B)로 나타냈다.A calibration curve of Atmer 163 (R = C 13 ) and a calibration curve of Atmer 163 (R = C 15 ) are shown in (A) and (B), respectively, in FIG.

6. 분석 결과 6. Analysis Results

Atmer 163(R=C13, R=C15)의 각 검량 곡선을 이용하여 계산한 결과는 다음과 같다(Atmer 163의 LOD: 0.1ppm)The calculation results using the calibration curves of Atmer 163 (R = C 13 , R = C 15 ) are as follows (LOD of Atmer 163: 0.1 ppm)

Figure pat00004
Figure pat00004

Atmer 163(R=C13) 표준 용액 및 시료의 LC/MS 추출된 이온 크로마토그램과 Atmer 163(R=C15) 표준 용액 및 시료의 LC/MS 추출된 이온 크로마토그램을 도 3에 각각 (A) 및 (B)로 나타냈다.The ion chromatogram of the Atmer 163 (R = C 13 ) standard solution and the LC / MS extracted ion chromatogram of the sample, the Atmer 163 (R = C 15 ) standard solution and the LC / MS extracted ion chromatogram of the sample are shown in ) And (B).

도 3에 근거하여 살펴 보면, 시료 Atmer 163(R=C13) 및 Atmer 163(R=C15)의 머무름 시간은 표준 용액에 대한 LC/MS 추출된 이온 크로마토그램과 거의 동일하게 각각 15.3분 및 17.0분임을 알 수 있다. 따라서, 본 발명의 분석방법에 따르면 담지 촉매 제조 공정 중 대전방지제를 포함한 헥산 여액 내 Atmer 163의 존재 여부 및 함량을 정확히 분석할 수 있다.3, the retention times of the samples Atmer 163 (R = C 13 ) and Atmer 163 (R = C 15 ) were almost the same as those of LC / MS extracted from the standard solution at 15.3 minutes and 17.0 minutes can be known. Therefore, according to the analysis method of the present invention, the presence and content of Atmer 163 in the hexane filtrate containing the antistatic agent during the supported catalyst production process can be accurately analyzed.

이상에서는 본 발명에 따른 바람직한 실시양태를 기술하였으나, 이는 예시적인 것이며 당업계의 통상의 지식을 가진 자라면 이에 의해 본 발명의 범위가 제한되는 것이 아니고 이로부터 다양한 변형 및 균등한 다른 실시양태가 가능하다는 점을 이해할 수 있을 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. You can understand that. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

비스(2-하이드록시에틸)알킬아민(bis(2-hydroxyethyl)alkylamine) 대전방지제를 포함하는 담지 촉매 제조 공정 중 헥산 여액을 HPLC/MS로 분석하는 것을 포함하는, 대전방지제의 함량 분석방법.A method for analyzing the content of an antistatic agent, which comprises analyzing a hexane filtrate by HPLC / MS in a supported catalyst production process comprising bis (2-hydroxyethyl) alkylamine antistatic agent. 제1항에 있어서, 아세톤(acetone)으로 희석한 상기 대전방지제 함유 표준 용액을 HPLC/MS로 분석하고 담지 촉매 제조 공정 중 상기 대전방지제를 포함한 헥산 여액을 니트(neat)로 HPLC/MS로 분석한 다음, 상기 표준 용액의 HPLC/MS 크로마토그램(chromatogram) 상에서 피크 면적을 계산하고 상기 헥산 여액에 대해서도 피크 면적을 계산한 다음, 각각의 검정 곡선(calibration)에 대입하여 시료 내 대전방지제의 농도를 계산하는 것을 포함하는, 분석방법.The method according to claim 1, wherein the standard solution containing the antistatic agent diluted with acetone is analyzed by HPLC / MS, and the hexane filtrate containing the antistatic agent is analyzed by neat analysis by HPLC / MS Next, the peak area is calculated on the HPLC / MS chromatogram of the standard solution, the peak area is calculated for the hexane filtrate, and the peak area is substituted for each calibration curve to calculate the concentration of the antistatic agent in the sample The method comprising the steps of: 제1항에 있어서, 상기 피크가 m/z=288 및 m/z=316으로 추출된 것인, 분석방법.2. The assay method according to claim 1, wherein said peak is extracted with m / z = 288 and m / z = 316. 제1항에 있어서, 상기 대전방지제가 화학식
Figure pat00005
의 Atmer 163인 것인, 분석방법.The positive resist composition according to claim 1,
Figure pat00005
The Atmer 163 is an analytical method. 제4항에 있어서, 상기 Atmer 163이 R=C13 구조와 R=C15 구조의 혼합물의 구조인 것인, 분석방법.5. The method according to claim 4, wherein the Atmer 163 is a structure of a mixture of R = C 13 structure and R = C 15 structure. 제1항에 있어서, 상기 대전방지제의 함량을 아래 식에 따라 계산하는 것인, 분석방법:
대전방지제의 함량(ppm, μg/ml) = Ccal
위의 식에서, Ccal은 검량 곡선에서 검출된 피크의 면적을 대입하여 구한 농도이다.The analytical method according to claim 1, wherein the content of the antistatic agent is calculated according to the following formula:
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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