KR100942314B1 - Measurement method for purity of didecyl-dimethyl-ammonium chloride using hplc-ms - Google Patents

Measurement method for purity of didecyl-dimethyl-ammonium chloride using hplc-ms Download PDF

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KR100942314B1
KR100942314B1 KR1020090023245A KR20090023245A KR100942314B1 KR 100942314 B1 KR100942314 B1 KR 100942314B1 KR 1020090023245 A KR1020090023245 A KR 1020090023245A KR 20090023245 A KR20090023245 A KR 20090023245A KR 100942314 B1 KR100942314 B1 KR 100942314B1
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hplc
ammonium chloride
ddac
dimethyl
didecyl
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강승모
김석권
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대한민국
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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
    • G01N30/02—Column chromatography
    • 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
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • 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
    • G01N30/02—Column chromatography
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    • G01N2030/027—Liquid chromatography

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Abstract

PURPOSE: A method of measuring purity of a didecyl-dimethyl-ammonium chloride is provided to reduce an additional pretreatment or a derivative action, and to accurately analyze a very small amount of component. CONSTITUTION: A method of measuring purity of a didecyl-dimethyl-ammonium chloride using a HPLC-MS comprises the following steps of: inserting the didecyl-dimethyl-ammonium chloride into the HPLC-MS; and deciding the didecyl-dimethyl-ammonium chloride inserted into the HPLC-MS is pure, if a HPLC-MS scan mode of the didecyl-dimethyl-ammonium chloride and a single ion mode shows the same peak, and peak with a molecular weight of 326m/z.

Description

고압액체크로마토그램 질량분석기를 이용한 다이데실-다이메틸-암모니움 클로라이드의 순도 측정방법{Measurement method for purity of didecyl-dimethyl-ammonium chloride using HPLC-MS}Measurement method for purity of didecyl-dimethyl-ammonium chloride using high pressure liquid chromatogram mass spectrometer {Measurement method for purity of didecyl-dimethyl-ammonium chloride using HPLC-MS}

본 발명은 고압액체크로마토그램 질량분석기(HPLC-MS)를 이용한 다이데실-다이메틸-암모니움 클로라이드(didecyl-dimethyl-ammonium chloride, DDAC)의 순도 측정방법에 관한 것으로 보다 상세하게는 고압액체크로마토그램 질량분석기(HPLC-MS)를 이용하여 목재용 대체 방부제로 사용하는 암모니칼 구리 제4급암모늄 화합물(Ammoniacal cooper quartz, ACQ) 중 ACQ type-2(ACQ-2)의 주성분인 다이데실-다이메틸-암모니움 클로라이드(DDAC)의 순도를 정성 및/또는 정량하고 미량의 성분까지 분석할 수 있는 방법에 관한 것이다.The present invention relates to a method for measuring purity of didecyl-dimethyl-ammonium chloride (DDAC) using a high pressure liquid chromatography mass spectrometer (HPLC-MS). Didecyl-dimethyl, the main component of ACQ type-2 (ACQ-2), in ammoniacal cooper quartz (ACQ) used as an alternative preservative for wood by mass spectrometry (HPLC-MS) It relates to a method that can qualitatively and / or quantify the purity of ammonium chloride (DDAC) and analyze even trace components.

목재는 천연소재이기 때문에 여러 가지 이유로 인해 부패가 진행되어 목재의 수명이 점점 짧아진다. 이러한 목재의 부패를 억제하며, 보존하기 위해 목재에 방부제를 처리하고 있다.Because wood is a natural material, it decays for a variety of reasons, resulting in a shorter life span of wood. To prevent the decay of the wood, preservatives are treated on the wood to preserve.

종래 목재용 방부재는 CCA(Chromated Copper Arsenate)를 많이 사용하였으나, 다양한 연구에 의해 CCA가 인체에 유해할 가능성이 있다고 하여 최근에는 CCA의 사용이 금지됨에 따라 CCA를 대체하기 위해 목재용 방부제로 주로 구리아민계 방부제인 copper azole, ammoniacal cooper quatz, copper cu-HDO 등이 사용되고 있으며, 이중 국내 방부처리 시장에서 방부처리목재의 80％ 이상이 ammoniacal cooper quartz(ACQ)에 의하여 처리되고 있다.Conventional wood preservatives have used CCA (Chromated Copper Arsenate) a lot, but various studies suggest that CCA may be harmful to the human body, so the use of CCA has recently been banned. Amine preservatives such as copper azole, ammoniacal cooper quatz and copper cu-HDO are used, and more than 80% of the preservative wood is treated by ammoniacal cooper quartz (ACQ) in the domestic antiseptic treatment market.

탁월한 목재용 방부제 중 하나인 ACQ는 여러 다른 형태로 제조되어 사용되고 있다. ACQ는 두 가지 유효 성부 성분을 포함하고 구리와 제4급암모늄화합물(quaternary ammonium compounds, quatz)의 다양한 구성비에 의하여 분류되고 있으며(AWPA, 2006), 주로 다이데실-다이메틸-암모니움 클로라이드(didecyl-dimethyl-ammonium chloride, DDAC)를 주성분으로 하는 ACQ type-2(ACQ-2), 벤질-다이메틸-도데실-암모니움클로라이드(Benzyl-dimethyl-dodecyl-ammoniumchloride, DBAC)를 주성분으로 하는 ACQ type-1(ACQ-1) 등이 사용되고 있다.ACQ, one of the best wood preservatives, is manufactured and used in many different forms. ACQ contains two active ingredients and is classified by various compositional ratios of copper and quaternary ammonium compounds (quatz) (AWPA, 2006), mainly didecyl-dimethyl-ammonium chloride (didecyl). ACQ type-2 (ACQ-2) mainly composed of -dimethyl-ammonium chloride (DDAC) and benzyl-dimethyl-dodecyl-ammonium chloride (DBAC) -1 (ACQ-1) and the like are used.

제4급암모늄화합물(quatz)은 미생물의 성장을 조절하는 냉각수 시스템, 살균제과 소독제, 부식억제제, 헤어린스, 분산제와 섬유유연제 같은 비산화성 살균제처럼 넓게 사용된다(Laopaiboon et al., 2002). 목재 방부제로 사용되는 ACQ 중에서 quatz는 주성분으로 Didecyldimethyl ammonium chloride(DDAC)를 사용하는 ACQ type-2(ACQ-2)와 주성분으로 Benzyl-dimethyl-dodecyl-ammoniumchlorid(DBAC)를 사용하는 ACQ type-1(ACQ-1)가 있다.Quaternary ammonium compounds (quatz) are widely used as non-oxidative fungicides, such as cooling water systems, fungicides and disinfectants, corrosion inhibitors, hair rinses, dispersants and fabric softeners that control microbial growth (Laopaiboon et al., 2002). Among the ACQs used as wood preservatives, quatz is ACQ type-2 (ACQ-2) using Didecyldimethyl ammonium chloride (DDAC) and ACQ type-1 (DBAC) using Benzyl-dimethyl-dodecyl-ammoniumchlorid (DBAC) as the main component. ACQ-1).

최근 들어서는 목재보존 산업 뿐만 아니라 목재 방부제가 방부물질을 포함하 기 때문에 정부 및 환경단체에서의 관심 또한 증가하고 있다. 국내 목재 방부 산업에서 quartz의 사용이 급증하고 있으므로 quartz 성분에 대해 정밀하고 재현성이 높은 순도 측정 방법의 개발이 요구되고 있다.Recently, as wood preservatives contain preservatives as well as the wood preservation industry, interest in the government and environmental groups is also increasing. As the use of quartz is rapidly increasing in the domestic wood preservation industry, it is required to develop a precise and reproducible purity measuring method for quartz components.

오랫동안 전통적인 적정법(titration method)이 QACs(quaternary ammonium chloride)의 정량에 적용되고 있지만, ACQ-2의 주성분인 Didecyl dimethyl ammonium chloride(DDAC)와 ACQ-1의 주성분인 Benzyl-dimethyl-dodecyl-ammoniumchloride(DBAC)를 분별하여 분석하지 못하고 또한 미량 성분의 분석이 불가능하였다. 또한 일반적인 고압액체크로마토그램 방법으로는 발색단이 존재하지 않는 Didecyldimethyl ammonium chloride(DDAC) 분석이 매우 어려워 부가적인 전처리와 유도체를 생성하여야 한다. 그리고 DDAC 단목 분석과 달리 ACQ는 강력한 양이온인 구리를 함유하기 때문에 이온 크로마토그램에 의한 분리 또한 매우 어렵다.Although traditional titration methods have long been used to quantify quaternary ammonium chloride (QACs), Didecyl dimethyl ammonium chloride (DDAC), the main component of ACQ-2, and Benzyl-dimethyl-dodecyl-ammonium chloride (DBAC), the main component of ACQ-1. ) Cannot be analyzed separately, and trace components cannot be analyzed. In addition, Didecyldimethyl ammonium chloride (DDAC) analysis without chromophore is very difficult by high pressure liquid chromatogram method, and additional pretreatment and derivatives should be generated. And unlike DDAC single item analysis, since ACQ contains copper, a strong cation, separation by ion chromatogram is also very difficult.

최근 대체 에너지의 개발과 사용이 급증함에 따라 알코올계의 값이 급등하여 중국을 중심으로 DDAC의 순도가 떨어지는 저급 DDAC의 사용과 유통이 증가하며 국내에서도 이러한 문제가 발생하고 있다. 그러나 이러한 유사 Quartz는 적정법에서는 DDAC와 구별이 불가능하고 HPLC법에서는 검출이 되지 않아 지금까지 적정법과 HPLC 분석값이 큰 차이를 나타는 것을 밝혀내지 못하고 있다.Recently, as the development and use of alternative energy has soared, the price of alcohol has soared, and the use and distribution of low-grade DDAC, which is less pure of DDAC, has increased in China. However, the similar quartz is indistinguishable from DDAC in the titration method and is not detected by the HPLC method. Thus, it has not been found that the difference between the titration method and the HPLC analysis shows a big difference.

이에 본 발명은 고압액체크로마토그램 질량분석기를 이용하면 부가적인 전처리와 유도체화 없이 목재용 대체 방부제로 사용하는 암모니칼 구리 제4급암모늄 화합물(Ammoniacal cooper quartz, ACQ) 중 ACQ type-2(ACQ-2)의 주성분인 다이데실-다이메틸-암모니움 클로라이드(DDAC)의 순도를 정성 및/또는 정량하고 미량의 성분 까지 분석도 정확하고 재현하고자 한다.Therefore, the present invention is based on the high-pressure liquid chromatogram mass spectrometer, ACQ type-2 (ACQ-) of ammoniacal quaternary ammonium compound (Ammoniacal cooper quartz, ACQ) used as an alternative preservative for wood without additional pretreatment and derivatization The purity of didecyl-dimethyl-ammonium chloride (DDAC), the main component of 2), is quantitatively and / or quantitated, and the analysis is accurate and reproduced up to the trace amount.

본 발명은 목재 방부제의 성분인 Didecyldimethyl ammonium chloride(DDAC)의 순도를 정성 및/또는 정량하는 방법의 제공을 목적으로 한다.An object of the present invention is to provide a method for qualitatively and / or quantifying the purity of Didecyldimethyl ammonium chloride (DDAC), a component of wood preservatives.

본 발명은 고압액체크로마토그램 질량분석기(HPLC-MS)를 이용하여 목재용 대체 방부제로 사용하는 암모니칼 구리 제4급암모늄 화합물(Ammoniacal cooper quartz, ACQ) 중 ACQ type-2(ACQ-2)의 주성분인 다이데실-다이메틸-암모니움 클로라이드(DDAC)의 순도를 정성 및/또는 정량하고 미량의 성분까지 분석할 수 있는 방법에 관한 것이다.The present invention relates to the use of ACQ type-2 (ACQ-2) in ammoniacal quaternary ammonium compound (Ammoniacal cooper quartz, ACQ) used as an alternative preservative for wood using high pressure liquid chromatography mass spectrometry (HPLC-MS). The present invention relates to a method for qualitatively and / or quantifying the purity of the main component, didecyl-dimethyl-ammonium chloride (DDAC), and analyzing the trace component.

본 발명의 고압액체크로마토그램 질량분석기를 이용하면 부가적인 전처리와 유도체화 없이 목재용 CCA 대체 방부제로 사용하는 암모니칼 구리 제4급암모늄 화합물(Ammoniacal cooper quartz, ACQ) 중 ACQ type-2(ACQ-2)의 주성분인 다이데실-다이메틸-암모니움 클로라이드(DDAC)의 순도를 정성 및/또는 정량하고 미량의 성분까지 분석도 정확하고 재현성 있게 할 수 있다. The high-pressure liquid chromatogram mass spectrometer of the present invention allows the use of ACQ type-2 (ACQ-) in ammoniacal quaternary ammonium compound (Ammoniacal cooper quartz, ACQ), which is used as an alternative preservative for wood CCA without additional pretreatment and derivatization. The purity of didecyl-dimethyl-ammonium chloride (DDAC), the main component of 2), can be qualitatively and / or quantified, and the analysis can be accurate and reproducible up to the trace amount.

본 발명은 고압액체크로마토그램 질량분석기를 이용하여 목재 방부제용 다이데실-다이메틸-암모니움 클로라이드의 순도 측정방법을 나타낸다.The present invention shows a method for measuring the purity of didecyl-dimethyl-ammonium chloride for wood preservatives using a high pressure liquid chromatography mass spectrometer.

본 발명은 고압액체크로마토그램 질량분석기를 이용하여 목재 방부제용 다이데실-다이메틸-암모니움 클로라이드의 정성 및/또는 정량하는 단계를 포함하는 고압액체크로마토그램 질량분석기를 이용하여 다이데실-다이메틸-암모니움 클로라이드의 순도 측정방법을 나타낸다.The present invention relates to a diedecyl-dimethyl- using a high pressure liquid chromatogram mass spectrometer comprising the step of qualitatively and / or quantifying diedecyl-dimethyl-ammonium chloride for wood preservatives using a high pressure liquid chromatogram mass spectrometer. The purity measurement of ammonium chloride is shown.

상기에서 순수한 다이데실-다이메틸-암모니움 클로라이드(DDAC)는 HPLC-MS의 스캔 모드(scan mode)와 싱글 이온 모드(single ion mode)가 동일한 피크가 형성된다.Pure didecyl-dimethyl-ammonium chloride (DDAC) has the same peak as the scan mode and single ion mode of HPLC-MS.

상기에서 순수하지 않은 다이데실-다이메틸-암모니움 클로라이드(DDAC)는 HPLC-MS의 스캔 모드(scan mode)와 싱글 이온 모드(single ion mode)가 동일하지 않은 피크가 형성된다. 일예로 순수하지 않은 저급의 다이데실-다이메틸-암모니움 클로라이드(DDAC)를 HPLC-MS으로 측정하는 경우, 싱글 이온 모드와 달리 스캔 모드에서 싱글 이온 모드와 다른 수개의 피크가 생성될 수 다.The non-pure didecyl-dimethyl-ammonium chloride (DDAC) forms peaks in which the scan mode and single ion mode of HPLC-MS are not the same. As an example, when pure lower didecyl-dimethyl-ammonium chloride (DDAC) is measured by HPLC-MS, several peaks may be generated in the scan mode unlike the single ion mode, unlike the single ion mode.

상기에서 순수한 다이데실-다이메틸-암모니움 클로라이드(DDAC)는 HPLC-MS에서 질량분석시 DDAC의 분자량 326m/z의 피크를 나타낸다.Pure didecyl-dimethyl-ammonium chloride (DDAC) shows a peak of 326 m / z molecular weight of DDAC in mass spectrometry on HPLC-MS.

상기에서 순수하지 않은 다이데실-다이메틸-암모니움 클로라이드(DDAC)는 HPLC-MS에서 질량분석시 DDAC의 분자량 326m/z의 피크를 나타내지 않고 다른 수치의 피크를 나타낸다.The non-pure didecyl-dimethyl-ammonium chloride (DDAC) does not show a peak of 326 m / z in molecular weight of DDAC in mass spectrometry in HPLC-MS, but shows a different peak.

상기에서 고압액체크로마토그램 질량분석기(HPLC-MS)는 HPLC(Prominence, Shimadzu/JP)와 MS(LCMS2010 EV, Shimadzu/JP)로 이루어진 것을 사용할 수 있다.The high-pressure liquid chromatogram mass spectrometer (HPLC-MS) may be made of HPLC (Prominence, Shimadzu / JP) and MS (LCMS2010 EV, Shimadzu / JP).

이하 본 발명의 내용을 아래의 실시예에 의하여 보다 상세히 설명하고자 한다. 그러나 이들 실시예는 본 발명의 내용을 보다 자세히 나타내는 것을 돕기 위한 것으로 이들에 의해 본 발명의 권리범위가 한정되는 것은 아니다.Hereinafter will be described in more detail by the following examples of the contents of the present invention. However, these examples are intended to help illustrate the contents of the present invention in more detail, and the scope of the present invention is not limited thereto.

<실시예 1><Example 1>

시그마-알드리치 케미칼(Sigma-Aldrich Chemicals) 회사로부터 Didecyl-dimethyl ammonium bromide(DDAB)를 구매하였다. 그리고 HPLC-UV 및 HPLC-MS 측정을 위해 각각 2-나프탈렌 설포닉 산 소디움 염(2-Naphthalene sulfonic acid sodium salt)(Wako Chemicals Co.)과 포름산 암모늄(Ammonium formate)(Junsei Chemicals Co.)를 준비하였다.Didecyl-dimethyl ammonium bromide (DDAB) was purchased from Sigma-Aldrich Chemicals. And 2-Naphthalene sulfonic acid sodium salt (Wako Chemicals Co.) and Ammonium formate (Junsei Chemicals Co.), respectively, for HPLC-UV and HPLC-MS measurements. It was.

(1)적정법(Titration method)(1) Titration method

적정법을 위해서 소디움 테트라페닐보레이트(sodium tetraphenylborate) 0.865g을 증류수(distilled water) 1ℓ에 희석하여 0.0025M STPB(Sodium Tetraphenylborate)를 준비하였고, 2',7'-다이클로로플루오레세인(2',7'-Dichlorofluorescein) 0.1g을 이소프로필 알코올(isopropyl alcohol) 100㎖에 희석하여 0.1％ 2',7'-Dichlorofluorescein를 준비하였다. 인산(Phosphoric acid) 20㎖와 증류수 80㎖를 혼합하여 20％ Phosphoric acid를 준비하였다.For titration, 0.865 g of sodium tetraphenylborate was diluted in 1 L of distilled water to prepare 0.0025M STPB (Sodium Tetraphenylborate), and 2 ', 7'-dichlorofluorescein (2', 7) 0.1 g of '-Dichlorofluorescein) was diluted in 100 ml of isopropyl alcohol to prepare 0.1% 2', 7'-Dichlorofluorescein. 20% Phosphoric acid was prepared by mixing 20 ml of phosphoric acid and 80 ml of distilled water.

ACQ 원액, ACQ 작업액 그리고 DDAC 분석 용액을 넣은 비커에 증류수 25㎖을 넣고 잘 섞어준 후 20％ Phosphoric acid를 이용해 용액의 pH 7로 맞추었다. 0.1％ 2',7'-Dichloroflutorescein을 스포이드로 14방울 떨어뜨린 후 0.0025M STPB를 첨가하면서 용액의 색이 연두색으로 완전히 변한 시점의 양을 기록하였다.25 ml of distilled water was added to a beaker containing the ACQ stock solution, the ACQ working solution, and the DDAC assay solution, and the mixture was mixed well and adjusted to pH 7 using 20% Phosphoric acid. 14 drops of 0.1% 2 ', 7'-Dichloroflutorescein was dropped with an eyedropper, and then 0.0025M STPB was added, and the amount of time point at which the color of the solution completely turned green was recorded.

％ Quatz의 양은 다음식에 의하여 계산되었다.The amount of% Quatz was calculated by the following equation.

1. Hyamine concentrationHyamine concentration

M Hyamine = Hyamine mass(g)/448.1M Hyamine = Hyamine mass (g) / 448.1

2. Sodium tetraphenylboron concentrationSodium tetraphenylboron concentration

M STPB = (M Hyamine) × (㎖ Hyamine)/㎖ STPB addedM STPB = (M Hyamine) × (ml Hyamine) / ml STPB added

3. ％ Quatz in solution:3.% Quatz in solution:

％ Quatz = (㎖ STPB) × (M STPB) × MW/10 × (sample mass, g)% Quatz = (ml STPB) × (M STPB) × MW / 10 × (sample mass, g)

MW DDAC = 362.1 g/molMW DDAC = 362.1 g / mol

MW DBAC = 354 g/molMW DBAC = 354 g / mol

(2)HPLC-UV(2) HPLC-UV

HPLC-UV에 사용되는 system은 3개의 펌프, 오토 샘플러, 컬럼 부분으로 구성되어 있었다. 이동상을 1.0㎖/min의 속도로 흐르게 하여 250×4.6mm(길이×직경)의 4.6㎛ ODS계 컬럼을 이용해 분리하였다. 이때 HPLC 컬럼 오븐의 온도는 40℃를 유지시켰다.The system used for HPLC-UV consisted of three pumps, an autosampler and a column part. The mobile phase was flowed at a rate of 1.0 mL / min and separated using a 250 × 4.6 mm (length × diameter) 4.6 μm ODS column. At this time, the temperature of the HPLC column oven was maintained at 40 ℃.

상기에서 이동상은 메탄올(methanol)과 버퍼(buffer)가 80:20의 부피비율로 하였다. 주입 볼륨은 10㎕로 설정했고 다이오드 검출기는 275㎚의 파장으로 설정하였다.In the mobile phase, methanol and a buffer were used in a volume ratio of 80:20. The injection volume was set to 10 μl and the diode detector was set to a wavelength of 275 nm.

상기의 이동상 중에서 버퍼(buffer)는 500㎖ 볼륨에 sodium dihydrogenphosphate 780㎎과 10％ Phosphoric acid 2㎖, 25mM 2-Naphthalene sulfonic acid sodium salt 10㎖를 넣어 혼합한 것을 사용하였다.Among the mobile phases, a buffer was prepared by mixing 780 mg of sodium dihydrogenphosphate, 2 ml of 10% Phosphoric acid, and 10 ml of 25 mM 2-Naphthalene sulfonic acid sodium salt in 500 ml volume.

ACQ 원액, ACQ 작업액 그리고 DDAC 분석 용액 1㎕를 오토 샘플러를 사용하여 HPLC-MS 시스템으로 주입하였다. 표준용액의 유효성은 검출한계(LOD)와 정량한계(LOQ)의 계산을 위해서 ICH Q2B의 유효 methodology로부터 결과를 구했다(ICH Q2B Validation of Analytical Procedures, 1996). 정성 방법은 처리용액과 DDAC로 방부 처리된 목재에 적용하는데 유효하도록 설정하였다.1 μl of ACQ stock, ACQ working solution and DDAC assay solution were injected into the HPLC-MS system using an autosampler. The validity of the standard solution was obtained from the effective methodology of ICH Q2B for the calculation of detection limit (LOD) and limit of quantification (LOQ) (ICH Q2B Validation of Analytical Procedures, 1996). The qualitative method is set to be effective for the treatment solution and wood treated with DDAC.

(3)HPLC-MS(3) HPLC-MS

HPLC(Prominence, Shimadzu/JP)와 MS(LCMS2010 EV, Shimadzu/JP)로 이루어진 HPLC-MS system은 electrospray ionization(ESI) 시스템을 구성하고 있으며, 액체크로마토그래피 매스 스펙트럼 시스템에 사용되는 75×4.6mm(길이×직경)의 4.6㎛ ODS계 측정 컬럼을 이용하여 분리하였다. 매스 스펙트럼(MS)은 선택 이온 모드(selectivity ion mode)와 양이온 모드(positive ion mode) 하에서 작동되었다. 질소는 1.5L/min으로 가스로 분무되어 흐르도록 하고 HPLC-MS의 interface 온도는 250℃, Curved Desolvation Line(CDL) 온도는 230℃로 설정하였고, Nebulizing gas flow는 1.5L/min, Heating Block의 온도는 200℃, Detector voltage는 1.2㎸ 그리고 칼럼오븐 온도는 40℃로 조정하였다.The HPLC-MS system, consisting of HPLC (Prominence, Shimadzu / JP) and MS (LCMS2010 EV, Shimadzu / JP), constitutes an electrospray ionization (ESI) system and is used for liquid chromatography chromatography. Length × diameter) and separated using a 4.6 μm ODS-based measurement column. The mass spectrum (MS) was operated under selective ion mode and positive ion mode. Nitrogen was sprayed into the gas at 1.5 L / min and flowed. The interface temperature of HPLC-MS was set to 250 ° C, the Curved Desolvation Line (CDL) temperature was set to 230 ° C, and the nebulizing gas flow was set to 1.5L / min and the heating block. The temperature was adjusted to 200 ° C, the detector voltage to 1.2㎸ and the column oven temperature to 40 ° C.

이동상은 0.5㎖/min으로 흘려주었으며, 상기 이동상은 HPLC용 isopropyl alcohol 100％인 A와 아세토니트릴(acetonitirle)과 버퍼(buffer)를 55:45로 혼합 한 B로 구성하였다. 이때 버퍼(buffer)는 100mM ammonium formate를 아세트산(acetic acids)를 이용하여 pH 3.7로 조절한 것을 사용하였다.The mobile phase was flowed at 0.5 mL / min, and the mobile phase consisted of A, which is 100% isopropyl alcohol for HPLC, acetonitrile (acetonitirle), and a buffer (B) with 55:45. At this time, the buffer (buffer) 100mM ammonium formate was adjusted to pH 3.7 using acetic acid (acetic acids) was used.

Binary gradient 프로그램은 이동상인 A와 B를 30:70의 부피 비율로 2분간 흘리고 점진적으로 isopropyl alcohol의 함량을 증가시켜 15분에는 100％의 isopropyl alcohol인 이동상 A를 적용하였고 3분 동안 이를 고정하였다. 그리고 마지막 단계로 다음 분석시료를 위하여 18분부터 30분까지 다시 이동상 A와 이동상 B를 30:70의 부피비율로 흘려 이동상을 초기화 하였다(도 1 참조).In the binary gradient program, mobile phases A and B were flowed at a volume ratio of 30:70 for 2 minutes and gradually increased the content of isopropyl alcohol. At 15 minutes, 100% isopropyl alcohol was applied to mobile phase A and fixed for 3 minutes. Finally, the mobile phase was initialized by flowing the mobile phase A and the mobile phase B at a volume ratio of 30:70 from 18 minutes to 30 minutes for the next analysis sample (see FIG. 1).

ACQ 원액, ACQ 작업액 그리고 DDAC 분석 용액 1㎕를 오토 샘플러를 사용하여 HPLC-MS 시스템으로 주입하였다. 표준용액의 유효성은 검출한계(LOD)와 정량한계(LOQ)의 계산을 위해서 ICH Q2B의 유효 methodology로부터 결과를 구했다(ICH Q2B Validation of Analytical Procedures, 1996). 정성 방법은 처리용액과 DDAC로 방부 처리된 목재에 적용하는데 유효하도록 설정하였다.1 μl of ACQ stock, ACQ working solution and DDAC assay solution were injected into the HPLC-MS system using an autosampler. The validity of the standard solution was obtained from the effective methodology of ICH Q2B for the calculation of detection limit (LOD) and limit of quantification (LOQ) (ICH Q2B Validation of Analytical Procedures, 1996). The qualitative method is set to be effective for the treatment solution and wood treated with DDAC.

(4)결과(4) results

직선상의 검량선은 5∼100(㎛/㎖)의 범위 안에서 각각의 다른 다섯 개의 점에 의해 실시되었다. HPLC-MS method는 DDAC 측정에서 HPLC-UV 보다 감도가 더 좋은 결과를 나타내었다(표 1 참조). LOD와 LOQ의 두 값은 HPLC-MS method에서 약 3배 우수하게 차이가 났다. 따라서 HPLC-MS method는 민감도와 정확도가 더 높기 때문에 ppb 단위까지 검출하는데 사용될 수 있다.The calibration curve on a straight line was carried out by five different points in the range of 5 to 100 (µm / ml). The HPLC-MS method showed better sensitivity than HPLC-UV in DDAC measurements (see Table 1). The two values of LOD and LOQ were about three times better in the HPLC-MS method. Therefore, the HPLC-MS method can be used to detect up to ppb because of its higher sensitivity and accuracy.

비록 HPLC-UV method가 ion paring 시약을 사용해서 인위적인 발색단을 유도체화 하였지만 ion paring 비율이 달라질 수 있어 실제의 분석치 보다 낮은 값의 측정값이 나올 수 있으며 재현성이 떨어질 수 있다(표 2 참조).Although the HPLC-UV method derivatizes the artificial chromophore using ion paring reagents, the ion paring ratio may vary, resulting in lower values than the actual analytical values and inferior reproducibility (see Table 2).

HPLC-MS는 선택적 이온 모드(SIM)를 이용해 선택된 분자만의 측정이 가능하고, 이것은 더 높은 민감도와 정확한 측정값을 얻어내었다(도 3 참조). HPLC-UV는 DDAC의 보유시간(target retention time)에 목재 추출물이나 다른 구성물질에 의한 간섭과 같은 잠재적인 문제점을 갖는데 반하여 HPLC-MS method는 정확도를 가지고 이러한 문제점을 성공적으로 제거할 수 있었다.HPLC-MS enabled selective ion mode (SIM) to measure only selected molecules, which yielded higher sensitivity and accurate measurements (see FIG. 3). While HPLC-UV has potential problems such as interference by wood extracts or other components at the target retention time of DDAC, the HPLC-MS method has been able to successfully eliminate this problem with accuracy.

적정법(Titration method)은 주관적인 측정 기술에 의지하기 때문에 분석저들 간의 차이가 나타날 수 있다(표 2 참조). 목재보존제인 ACQ에 사용되는 DDAC는 95％의 C10과 다른 동족체들로 이루어져서 있다. HPLC 분석법은 표준물질인 C10만을 측정하기 때문에, 적정법 보다 낮은 값이 나타난다(표 2 참조).Because the titration method relies on subjective measurement techniques, differences between assays may appear (see Table 2). The DDAC used in the wood preservative ACQ is composed of 95% C10 and other homologues. Since HPLC analysis only measures the standard C10, lower values are shown than the titration method (see Table 2).

표 1. HPLC-UV와 HPLC-MS에 의한 DDAC의 LODs와 LOQs. TABLE 1 LODs and LOQs of DDAC by HPLC-UV and HPLC-MS.

항목Item LOD(㎍/㎖)LOD (μg / ml) LOQ(㎍/㎖)LOQ (μg / ml) HPLC-UVHPLC-UV 2.662.66 8.058.05 HPLC-MSHPLC-MS 0.830.83 2.522.52

표 2. 적정(Titration), HPLC-UV와 HPLC-MS에 의한 처리 용액안의 DDAC 농도(％) 측정.Table 2. Determination of DDAC concentration (%) in the treatment solution by titration, HPLC-UV and HPLC-MS.

Treating solutionTreating solution TitrationTititation HPLC-UVHPLC-UV HPLC-MSHPLC-MS ACQ-2 (DDAC)ACQ-2 (DDAC) 1One 7.0(0.310)* 7.0 (0.310) * 5.31(0.003)5.31 (0.003) 6.38(0.122)6.38 (0.122) 22 5.85(0.48)5.85 (0.48) 1.06(0.038)1.06 (0.038) 1.28(0.015)1.28 (0.015) 33 4.74(0.210)4.74 (0.210) 3.80(0.001)3.80 (0.001) 4.45(0.058)4.45 (0.058)

* Numbers in parentheses represent the standard deviation * Numbers in parentheses represent the standard deviation

<실시예 2><Example 2>

최근 대체 에너지의 개발과 사용이 급증함에 따라 알코올계의 값이 급등하여 중국을 중심으로 DDAC의 순도가 떨어지는 저급 DDAC의 사용과 유통이 증가하며 국내에서도 이러한 문제가 발생하고 있다. 목재 방부제로 널리 사용되는 ACQ type2에는 DDAC를 사용하게 되어 있다. 이러한 유사 Quartz는 적정법에서는 DDAC와 구별이 불가능하고 HPLC법에서는 검출이 되지 않아 지금까지 적정법과 HPLC 분석값이 큰 차이를 나타는 것을 밝혀내지 못하고 있다. Recently, as the development and use of alternative energy has soared, the price of alcohol has soared, and the use and distribution of low-grade DDAC, which is less pure of DDAC, has increased in China. DDAC is used for ACQ type2, which is widely used as a wood preservative. Such quasi-quartz is indistinguishable from DDAC in titration method and cannot be detected by HPLC method. So far, it has not been found that there is a big difference between titration method and HPLC analysis value.

순수한 DDAC를 지니는 Quartz와 순수하지 않은 DDAC를 지니는 Quartz에 대해 상기 실시예 1의 (3)HPLC-MS에 기재된 내용을 이용하여 순수한 DDAC를 지니는 Quartz와 순수하지 않은 DDAC를 지니는 Quartz에 대한 정성 분석 및 정량 분석을 실시하였다. For qualitative quartz with pure DDAC and quartz with pure DDAC, qualitative analysis of quartz with pure DDAC and quartz with pure DDAC, using the contents described in (3) HPLC-MS of Example 1 above. Quantitative analysis was performed.

도 4는 HPLC-MS에서 싱글 이온 모드(Single ion mode)(아래쪽 그래프)와 스캔 모드(Scan mode)(위쪽 그래프) 동시 적용시 순수한 DDAC 크로마토그램이다. FIG. 4 is pure DDAC chromatogram upon simultaneous application of Single ion mode (bottom graph) and Scan mode (top graph) in HPLC-MS.

도 5는 HPLC-MS에서 싱글 이온 모드(Single ion mode)(아래쪽 그래프)와 스캔 모드(Scan mode)(위쪽 그래프) 동시 적용시 순수하지 않은 DDAC 크로마토그램이다.FIG. 5 is not pure DDAC chromatogram when applying Single ion mode (bottom graph) and Scan mode (top graph) simultaneously in HPLC-MS.

Single ion mode에서 DDAC의 분자량 326m/z을 이용하여 정성과 정량을 분석한다. Scan mode는 분자량을 50∼500m/z를 정하고 분석한 결과 DDAC외에 유사한 Quartz가 270m/z와 298m/z에서도 측정되었다(도 6a 내지 도 6c 참조). In single ion mode, qualitative and quantitative analysis is carried out using the molecular weight 326m / z of DDAC. In the scan mode, the molecular weight of 50 to 500 m / z was determined and analyzed, and similar quartz was measured at 270 m / z and 298 m / z in addition to DDAC (see FIGS. 6A to 6C).

도 6a는 HPLC-MS에서 순수 DDAC의 질량 분석(326m/z)을 나타낸 그래프이다.6A is a graph showing mass spectrometry (326 m / z) of pure DDAC in HPLC-MS.

도 6b는 HPLC-MS에서 순수하지 않은 DDAC의 질량 분석(298m/z)을 나타낸 그래프이다.6B is a graph showing mass spectrometry (298 m / z) of DDAC not pure in HPLC-MS.

도 6c는 HPLC-MS에서 순수하지 않은 DDAC의 질량 분석(270m/z)을 나타낸 그래프이다.6C is a graph showing mass spectrometry (270 m / z) of DDAC not pure in HPLC-MS.

따라서 본 HPLC-MS법에서는 DDAC 유사 Quartz를 성공적으로 분리 분석할 수 있다. Therefore, this HPLC-MS method can successfully separate and analyze DDAC-like quartz.

본 실험결과 HPLC-MS method에 의한 방법이 HPLC-UV보다 더 민감하고 명확한 결과를 나타냄을 보여주었다. HPLC-MS method는 목재보존처리용액과 방부처리목재 안에 DDAC를 성공적으로 분석할 수 있었다. 고압액체크로마토그램 질량분석기를 이용하면 Didecyldimethyl ammonium chloride(DDAC)를 부가적인 전처리와 유도체화 없이 간단히 분석하고 미량의 성분까지 분석이 가능하다. 또한 본 HPLC-MS법에서는 DDAC와 유사 Quartz를 분리 분석하여 적정법과 HPLC법의 한계를 극복할 수 있었다. ACQ 방부제 생산업체, 방부목재 생산업체, 그리고 시험기관에서 목재 방부제용 Didecyldimethyl ammonium chloride (DDAC)의 개발 및 품질관리에 이용할 수 있다. The results showed that the method by HPLC-MS method showed more sensitive and clear results than HPLC-UV. The HPLC-MS method was able to successfully analyze DDAC in preservative wood and preservative wood. The high pressure liquid chromatogram mass spectrometer allows simple analysis of Didecyldimethyl ammonium chloride (DDAC) without additional pretreatment and derivatization and analysis of trace components. In addition, this HPLC-MS method was able to overcome the limitations of titration and HPLC methods by separating and analyzing DDAC and similar quartz. ACQ preservative producers, preservative wood producers, and test laboratories can be used for the development and quality control of Didecyldimethyl ammonium chloride (DDAC) for wood preservatives.

상술한 바와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다. As described above, although described with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the invention described in the claims below. It will be appreciated that it can be changed.

본 발명의 고압액체크로마토그램 질량분석기를 이용하면 부가적인 전처리와 유도체화 없이 목재용 대체 방부제로 사용하는 암모니칼 구리 제4급암모늄 화합물(Ammoniacal cooper quartz, ACQ) 중 ACQ type-2(ACQ-2)의 주성분인 다이데실-다이메틸-암모니움 클로라이드(DDAC)의 순도를 정성 및/또는 정량하고 미량의 성분까지 분석도 정확하고 재현성 있게 할 수 있으므로 ACQ 방부제 생산업체, 방부목재 생산업체, 그리고 시험기관에서 목재 방부제용 Didecyldimethyl ammonium chloride(DDAC)의 개발 및 품질관리에 이용할 수 있다. The high pressure liquid chromatogram mass spectrometer of the present invention allows the use of ACQ type-2 (ACQ-2) in ammoniacal quaternary ammonium compound (Ammoniacal cooper quartz, ACQ) used as an alternative preservative for wood without additional pretreatment and derivatization. ACQ preservative producers, anticorrosive producers, and testers, as they can qualitatively and / or quantify the purity of didecyl-dimethyl-ammonium chloride (DDAC), the main component of It can be used for the development and quality control of Didecyldimethyl ammonium chloride (DDAC) for wood preservatives.

도 1은 바이너리 그래디언트(Binary gradient) 프로그램 이동상 A의 드로 커브(Draw curve)를 나타낸 그래프이다.FIG. 1 is a graph illustrating a draw curve of a binary gradient program mobile phase A. Referring to FIG.

도 2는 DDAC의 HPLC-UV 크로마토그램이다. 2 is an HPLC-UV chromatogram of DDAC.

도 3은 DDAC의 HPLC-MS 크로마토그램이다.3 is an HPLC-MS chromatogram of DDAC.

도 4는 HPLC-MS에서 싱글 이온 모드(Single ion mode)(아래쪽 그래프)와 스캔 모드(Scan mode)(위쪽 그래프) 동시 적용시 순수한 DDAC 크로마토그램이다. FIG. 4 is pure DDAC chromatogram upon simultaneous application of Single ion mode (bottom graph) and Scan mode (top graph) in HPLC-MS.

도 5는 HPLC-MS에서 싱글 이온 모드(Single ion mode)(아래쪽 그래프)와 스캔 모드(Scan mode)(위쪽 그래프) 동시 적용시 순수하지 않은 DDAC 크로마토그램이다.FIG. 5 is not pure DDAC chromatogram when applying Single ion mode (bottom graph) and Scan mode (top graph) simultaneously in HPLC-MS.

도 6a는 HPLC-MS에서 순수 DDAC의 질량 분석(326m/z)을 나타낸 그래프이다.6A is a graph showing mass spectrometry (326 m / z) of pure DDAC in HPLC-MS.

도 6b는 HPLC-MS에서 순수하지 않은 DDAC의 질량 분석(298m/z)을 나타낸 그래프이다.6B is a graph showing mass spectrometry (298 m / z) of DDAC not pure in HPLC-MS.

도 6c는 HPLC-MS에서 순수하지 않은 DDAC의 질량 분석(270m/z)을 나타낸 그래프이다.6C is a graph showing mass spectrometry (270 m / z) of DDAC not pure in HPLC-MS.

Claims (3)

고압액체크로마토그램 질량분석기(HPLC-MS)에 다이데실-다이메틸-암모니움 클로라이드(DDAC)를 주입한 후 다이데실-다이메틸-암모니움 클로라이드의 HPLC-MS 스캔 모드와 싱글 이온 모드가 동일한 피크가 형성되고, HPLC-MS에서 분자량 326m/z의 피크를 나타내면 HPLC-MS에 주입된 다이데실-다이메틸-암모니움 클로라이드가 순수한 것이라고 판단하는 것을 특징으로 하는 고압액체크로마토그램 질량분석기를 이용하여 다이데실-다이메틸-암모니움 클로라이드의 순도 측정방법.Injecting didecyl-dimethyl-ammonium chloride (DDAC) into a high pressure liquid chromatogram mass spectrometer (HPLC-MS) and then peaking the same HPLC-MS scan mode as the single ion mode of didecyl-dimethyl-ammonium chloride Is formed, and the peak of the molecular weight of 326 m / z in HPLC-MS is determined that the diedecyl-dimethyl-ammonium chloride injected into the HPLC-MS is determined to be pure using a high pressure liquid chromatogram mass spectrometer. Method for measuring purity of decyl-dimethyl-ammonium chloride. 삭제delete 삭제delete
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CN102707002A (en) * 2011-05-27 2012-10-03 广东美味鲜调味食品有限公司 Method for simultaneously measuring content of various preservatives in soy sauce by capillary gas chromatography internal standard method
CN102707002B (en) * 2011-05-27 2015-08-05 广东美味鲜调味食品有限公司 The method of various antiseptic content in capillary gas chromatography internal standard method Simultaneously test soy sauce
CN103728405A (en) * 2013-12-24 2014-04-16 中国检验检疫科学研究院 Research method of wood preservative migration rule in wooden children product
CN103728405B (en) * 2013-12-24 2016-12-07 中国检验检疫科学研究院 The research method of timber preservative Transport in a kind of Wood children articles for use
KR101636256B1 (en) * 2015-12-30 2016-07-08 충남대학교산학협력단 Color-assuming reagent for wood treated with preservative comprising didecyldimethylammonium chloride and method for coloring using the same
CN105911171A (en) * 2016-04-14 2016-08-31 梧州市产品质量检验所 Determination method for preservative in food
CN107976496A (en) * 2017-11-22 2018-05-01 苏州市金茂日用化学品有限公司 Benzoic acid, sorbic acid, salicylic acid and the method for Phenoxyethanol separation and content analysis in a kind of toothpaste
CN108548744A (en) * 2018-02-10 2018-09-18 安徽省产品质量监督检验研究院（国家排灌及节水设备产品质量监督检验中心） In a kind of wet tissue the simulation of isothiazolinone preservative using the rate of transform assay method
CN111337591A (en) * 2020-03-26 2020-06-26 生态环境部南京环境科学研究所 Method for measuring decamethylammonium chloride in soil

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