KR101260727B1 - Certified reference material for flame retardants in High impact polystyrene and manufacturing method - Google Patents
Certified reference material for flame retardants in High impact polystyrene and manufacturing method Download PDFInfo
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Abstract
본 발명은 난연제 측정용 고충격폴리스티렌 인증표준물질 및 그 제조방법에 관한 것으로, 더 상세하게는 난연성을 갖는 물품 특히 고충격폴리스틸렌이 주요재료로 사용되고 있는 전기전자용품에 함유된 난연제 량이 함량기준치 이상으로 포함되었는지를 판단할 수 있는 인증표준물질 및 그 제조방법에 관한 것이다. The present invention relates to a high impact polystyrene certified standard material for measuring flame retardant and a method for manufacturing the same. More specifically, the amount of the flame retardant contained in an electrical and electronic product in which a flame retardant, especially high impact polystyrene is used as a main material, is greater than or equal to the content standard value. The present invention relates to a certified standard material and a method of manufacturing the same, which can be determined whether or not it is included.
Description
본 발명은 난연제 측정용 고충격폴리스티렌 인증표준물질 및 그 제조방법에 관한 것으로, 더 상세하게는 난연성을 갖는 물품 특히 고충격폴리스틸렌이 주요재료로 사용되고 있는 전기전자용품에 함유된 난연제 량이 함량기준치 이상으로 포함되었는지를 판단할 수 있는 인증표준물질 및 그 제조방법에 관한 것이다.
The present invention relates to a high impact polystyrene certified standard material for measuring flame retardant and a method for manufacturing the same. More specifically, the amount of the flame retardant contained in an electrical and electronic product in which a flame retardant, especially high impact polystyrene is used as a main material, is greater than or equal to the content standard value. The present invention relates to a certified standard material and a method of manufacturing the same, which can be determined whether or not it is included.
일반적으로, 건축물과 전자제품등 다양한 분야에서 화재시 연소를 지연시키고 연기발생을 억제하는 제품이 사용되고 있다. 특히 재료의 사용용도와 규모에 따라 난연등급을 정하여 사용함으로써 화재시 피해를 최소화하고 있다. In general, in various fields such as buildings and electronic products, products that delay combustion and suppress smoke generation in a fire are used. In particular, the flame retardant grade is determined according to the usage and scale of materials to minimize the damage in case of fire.
예컨대 전기전자 제품에 브롬계 난연제 성분이 많이 포함되어 있을 경우 인체에 유해하고 제품을 사용한 후 폐기 시 환경을 오염시키는 등 문제점이 있으므로 유럽, 한국, 미구, 일본등은 제품 재료에 포함된 브롬계 난연제 함량을 1000 mg/kg 수준 이하의 농도를 갖도록 규제하고 있다. For example, if a large amount of bromine-based flame retardants are contained in electrical and electronic products, there is a problem such as harmful to human body and polluting the environment when using the product. The content is regulated to have a concentration below 1000 mg / kg.
상기 전기전자제품을 제조하는 주요재료로는 고충격폴리스티렌으로 이에 포함되어 있는 난연제의 함량을 측정하기 위해서는 상기 고충격폴리스티렌을 용매에 용해시키고 성분을 분리한 다음 난연제 성분만 추출하여 이를 측정함으로써 제품에 대한 난연제 함량 값을 알 수 있다. The main material for manufacturing the electrical and electronic products is a high impact polystyrene, in order to measure the content of the flame retardant contained therein, by dissolving the high impact polystyrene in a solvent, separating the components and then extracting only the flame retardant components to measure the product The flame retardant content value can be seen.
그러나 상기방법의 결과가 정확하기 위해서는 난연제측정의 기준이 되는 인증표준물질이 필수 적이나 아직까지 전기전자 주요 재료인 고충격폴리스티렌 중 난연제를 정확히 측정하는데 기준이 되는 난연제 측정용 인증표준물질이 없어 측정정확성이 떨어지는 문제점이 있었다.
However, in order for the results of the above method to be accurate, certification standard, which is a standard for flame retardant measurement, is essential.However, there is no certification standard for flame retardant measurement, which is the standard for accurately measuring flame retardant among high-impact polystyrene, which is a major electric and electronic material. There was a falling issue.
이에 본 발명의 난연제 측정용 고충격폴리스티렌 인증표준물질 및 그 제조방법은,The high-impact polystyrene certified standard material for measuring the flame retardant of the present invention and its manufacturing method,
고충격폴리스티렌 소재에 포함된 난연제성분을 측정할 수 있고, 제조과정에서 균질성 및 안정성을 확보하여 난연제 성분들의 함량을 정확하게 인증함으로써 기기 교정 및 분석법을 유효화 할 수 있는 고충격폴리스티렌에 포함된 난연제 측정용 인증표준물질 및 그 제조방법의 제공을 목적으로 한다.
Flame retardant component included in the high impact polystyrene material can be measured, and homogeneity and stability can be secured during the manufacturing process to accurately verify the content of the flame retardant components for measuring the flame retardant included in the high impact polystyrene which can validate instrument calibration and analysis methods. The purpose is to provide certified reference materials and methods for their preparation.
상기 과제를 해소하기 위한 본 발명의 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법은,Method for producing a high impact polystyrene certified standard material for flame retardant measurement of the present invention for solving the above problems,
고충격폴리스티렌 소재속에 포함된 난연제 성분을 정확하게 측정하기 위한 고충격폴리스티렌 인증표준물질 제조방법에 있어서, 고충격폴리스티렌과 난연제 또는 난연제혼합물을 칭량하여 혼합해 혼합시료를 제조하되, 상기 혼합시료의 난연제 농도를 측정기준농도의 10배에 해당하는 농도로 설정하는 마스터배치시료 난연제농도 설정과정과; 상기 혼합시료를 압출기로 투입하여 펠렛형태로 압출성형하고 이를 2~5회 반복하여 균질한 마스터배치시료를 제조하는 마스터배치시료 제조과정과; 상기 마스터배치시료를 칭량하고, 칭량된 마스터배치시료의 난연제성분 농도가 인증표준물질의 측정기준농도와 같아지도록 펠렛형태의 고충격폴리스티렌 소재를 칭량하여 혼합하는 인증표준물질용시료혼합물 제조과정과; 상기 인증표준물질용시료혼합물을 압출기에 투입하여 2~5회 압출성형하여 인증표준물질을 제조하는 인증표준물질성형과정;을 포함하여 이루어진다.In the method of manufacturing a high impact polystyrene certified standard material for accurately measuring the flame retardant component contained in the high impact polystyrene material, a high impact polystyrene and a flame retardant or a flame retardant mixture are weighed and mixed to prepare a mixed sample, but the flame retardant concentration of the mixed sample Setting a flame retardant concentration of the master batch sample to set the concentration to 10 times the concentration of the measurement standard; A process for producing a master batch sample by inserting the mixed sample into an extruder and extruding it into pellets to produce a homogeneous master batch sample by repeating it 2 to 5 times; Preparing a sample mixture for a certification standard material by weighing the master batch sample and weighing and mixing a high impact polystyrene material in pellet form such that the flame retardant component concentration of the weighed master batch sample is equal to the measurement standard concentration of the certified standard material; The certification standard material molding process for producing a certified standard material by inserting the sample mixture for the certified standard material into an
또한, 상기 인증표준물질성형과정에서 제조된 인증표준물질은 시료전처리법과 동위원소희석질량분석법에 의해 균질성, 안정성, 인증값의 불확도산출하여 적합성여부를 판단하는 검증과정이 더 이루어질 수 있다. In addition, the certification standard material manufactured in the certification standard material molding process may be further verified by determining the suitability by calculating the uncertainty of homogeneity, stability, and certification value by sample pretreatment and isotope dilution mass spectrometry.
아울러 본 발명의 난연제 측정용 고충격폴리스티렌 인증표준물질은,In addition, the high impact polystyrene certified standard material for flame retardant measurement of the present invention,
고충격폴리스티렌 소재속에 포함된 난연제 성분을 정확하게 측정하는데 사용되는 고충격폴리스티렌 인증표준물질에 있어서, 난연제 10~1000 mg과 잔량으로 고충격폴리스티렌 혼합된 혼합시료 1 kg에 대해 분산제 4000~6000 mg, 난연조제 30000~40000 mg가 균일하게 혼합되어 펠럿형태를 갖는 것을 특징으로 한다.
High-impact polystyrene-certified standard used to accurately measure the flame retardant component contained in the high-impact polystyrene material, with dispersant 4000-6000 mg per 1 kg of mixed sample of high-impact polystyrene mixed with 10 to 1000 mg of flame retardant and the remaining amount, flame retardant It is characterized in that the preparation 30000 ~ 40000 mg uniformly mixed to have a pellet form.
이상에서 상세히 기술한 바와 같이 본 발명의 난연제 측정용 고충격폴리스티렌 인증표준물질 및 그 제조방법은,As described in detail above, the high-impact polystyrene certified standard material for measuring the flame retardant of the present invention and a method of manufacturing the same,
전기전자 제품의 주성분인 고충격폴리스티렌 속재 속에 들어 있는 난연제 성분 측정시 기기의 교정 및 분석법의 유효화를 할 수 난연제 측정용 고충격폴리스티렌 인증표준물질의 제공이 가능하게 되었다. It is possible to provide a high-impact polystyrene certified standard for flame retardant measurement, which can validate the calibration and analysis of the flame retardant in the high-impact polystyrene component, which is the main component of electrical and electronic products.
또한, 본 발명의 인증표준물질은 고충격폴리스티렌 생산시 제품의 QC(Quality Control)/QA(Quality Assurance) 및 고충격폴리스티렌 부품의 환경 및 인체 안전성 보장을 위한 정밀 측정 등에 다양한 분야로의 활용될 수 있다.
In addition, the certification standard material of the present invention can be used in various fields, such as precision control to ensure the environment and human safety of the product quality control (QC) / Quality Assurance (QA) and high impact polystyrene components in the production of high impact polystyrene have.
도 1과 2는 본 발명의 실시예에 따른 인증표준물질 제조방법의 블록도이다.
도 3은 본 발명에서 제조하여 분리보관하는 인증표준물질들 간의 동질성을 측정한 그래프.1 and 2 is a block diagram of a method for manufacturing a certified standard material according to an embodiment of the present invention.
Figure 3 is a graph measuring the homogeneity between the certified standard materials prepared and stored in the present invention.
이하에서는 본 발명을 첨부된 도면과 함께 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail with the accompanying drawings.
도 1과 2는 본 발명의 실시예에 따른 인증표준물질 제조방법의 블록도이다.1 and 2 is a block diagram of a method for manufacturing a certified standard material according to an embodiment of the present invention.
도 1에 도시된 바와같이 본 발명에 따른 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법은, As shown in Figure 1 a high impact polystyrene certified standard material manufacturing method for measuring a flame retardant according to the present invention,
마스터배치시료 난연제농도설정과정과, 마스터배치시료 제조과정과, 인증표준물질용 혼합물제조과정과, 인증표준물질성형과정을 포함하여 이루어진다. It includes the process of setting the master batch sample flame retardant concentration, the process of manufacturing the master batch sample, the preparation of the mixture for certified standard materials, and the process of shaping the certified standard material.
상기 마스터배치시료의 난연제농도설정과정은 고충격폴리스티렌과 난연제(polybrominated diphenyl ether) 또는 난연제혼합물을 칭량하고 혼합하여 혼합시료를 제조하며, 상기 혼합시료의 난연제 농도를 최종적으로 제조될 인증표준물질의 측정기준농도 (인증값, 10 -1000 mg/kg)에 대해 약 10배의 농도(100 -10000 mg/kg)를 같도록 설정하는 과정이다. 예컨대 난연제와 고충격폴리스티렌의 혼합물 1kg의 혼합비는 난연제 100~10000mg과 잔량으로 고충격폴리스티렌을 혼합하는 비율로 제조된다. 또한, 상기 혼합은 균질하게 혼합하는 다양한 방법이 적용 될 수 있으며, 바람직하게는 콘믹서(con-mixer)를 사용하여 20분이상 충분하게 혼합하는 것이다. The flame retardant concentration setting process of the master batch sample is prepared by weighing and mixing a high impact polystyrene and a flame retardant (polybrominated diphenyl ether) or a flame retardant mixture to prepare a mixed sample, and the concentration of the flame retardant of the mixed sample is finally measured. It is a process to set the concentration (100-10000 mg / kg) of about 10 times the standard concentration (certified value, 10-1000 mg / kg). For example, a mixing ratio of 1 kg of a mixture of a flame retardant and high impact polystyrene is prepared at a ratio of 100 to 100 mg of flame retardant and high impact polystyrene in the remaining amount. In addition, the mixing may be applied to a variety of methods for mixing homogeneously, preferably a sufficient mixing for 20 minutes or more using a con-mixer (con-mixer).
또한, 상기 과정에서의 혼합시료에는 분산제와, 난연조제가 더 혼합될 수 있다. 일예로 분산제로는 칼슘스테아레이트(Ca[CH3(CH2)16CO2]2)를 사용하고, 난연조제로는 삼산화 안티몬 (Sb2O3)을 사용할 수 있다. 이와같이 고충격폴리스티렌, 난연제, 분산제, 난연조제가 혼합된 혼합시료의 혼합비로는 100~10000mg의 난연제에 고충격폴리스티렌을 잔량으로 혼합한 혼합시료 1kg에 대해 분산제 4000~6000 mg, 난연조제 30000~40000 mg을 혼합한다. 이때 상기 분산제와 난연조제는 균질한 혼합이전에 투입하여 균질화가 이루어지도록 하는 것이 바람직하다.
In addition, the dispersant and the flame retardant aid may be further mixed in the mixed sample in the above process. For example, calcium stearate (Ca [CH 3 (CH 2 ) 16 CO 2 ] 2 ) may be used as a dispersant, and antimony trioxide (Sb 2 O 3 ) may be used as a flame retardant aid. As such, the mixing ratio of the high impact polystyrene, flame retardant, dispersant, and flame retardant aid is mixed in the amount of 100 to 100 mg of flame retardant and 1 kg of the mixed sample containing the high impact polystyrene in the remaining amount, dispersant 4000 to 6000 mg, flame retardant aid 30000 to 40000 Mix mg. In this case, the dispersant and the flame retardant aid are preferably added before homogeneous mixing to allow homogenization.
다음으로 상기 마스터배치시료 제조과정은 상기 혼합시료를 압출기로 투입해 펠렛형태로 압출성형하여 제조된다. 상기 압출기의 바람직한 운전조건으로는 혼합시료를 10 kg/hr로 투입하고, 190 ℃에서 압출성형하여 펠렛 형태의 마스터배치시료가 제조되게 한 것이다.Next, the master batch sample manufacturing process is prepared by inserting the mixed sample into an extruder and extruding in pellet form. Preferred operating conditions of the extruder is to mix the sample at 10 kg / hr, and extrusion molding at 190 ℃ to prepare a master batch sample in the form of pellets.
또한, 상기 압출성형된 마스터배치시료를 다시 압출기로 투입하여 재압출성형이 이루어지게 하는 등 압출성형을 2~5회 반복실시하여 마스터배치시료의 균질도를 향상시킬 수 있다.
In addition, the extruded master batch sample is added to the extruder again to be extruded, such as repeated extrusion molding can be carried out 2 to 5 times to improve the homogeneity of the master batch sample.
상기 인증표준물질용 시료혼합물 제조과정은 상기 마스터배치시료 제조과정에서 수취한 마스터배치시료와 펠렛형태의 고충격폴리스티렌 소재를 칭량하여 혼합하는 과정이다. 즉, 수취한 마스터배치시료의 난연제 성분 농도를 인증표준물질의 측정기준농도가 되도록 혼합하는 과정이다. 상기 과정에서는 측정기준농도의 10배에 해당하는 농도를 가지는 마스터배치시료 1 kg에 대해 펠렛형태의 고충격폴리스티렌 소재 9 kg의 비율로 인증표준물질의 측정기준농도가 되게 혼합하는 과정이다. 이때 인증표준물질의 측정기준농도범위는 마스터배치시료 난연제 농도 설정과정에서 가하는 난연제의 무게(100-10000 mg)을 달리하여 조절할 수 있으며 또한 인증표준물질용 시료혼합물 제조과정에서 혼합하는 마스터배치시료와 펠렛형태의 고충격폴리스티렌 소재의 비율을 달리하여 조절할 수 있다. 혼합된 물질들은 혼합기를 통해 30분이상 충분히 혼합하여 마스터배치시료와 고충격폴리스티렌 소재가 충분히 균질하게 혼합되도록 한다.
The sample mixture manufacturing process for the certified standard material is a process of weighing and mixing a high-impact polystyrene material in a pellet form with the master batch sample received in the master batch sample manufacturing process. In other words, it is a process of mixing the concentration of the flame retardant component of the received master batch sample to the measurement standard concentration of the certified standard material. In the above process, 1 kg of the master batch sample having a concentration corresponding to 10 times the concentration of the measurement standard is mixed at a ratio of 9 kg of the pellets of high-impact polystyrene material in the form of a reference material. At this time, the measurement standard concentration range of the certified standard material can be adjusted by varying the weight of the flame retardant (100-10000 mg) applied in the process of setting the master batch sample flame retardant concentration, and the master batch sample mixed in the process of preparing the sample mixture for the certified standard material. It can be adjusted by varying the proportion of the high impact polystyrene material in the form of pellets. The mixed materials are thoroughly mixed for at least 30 minutes through a mixer to ensure that the master batch sample and the high impact polystyrene material are sufficiently homogeneously mixed.
상기 인증표준물질성형과정은 인증표준물질용 시료혼합물 제조과정에서 혼합된 마스터배치시료와 고충격폴리스티렌 소재 혼합물을 압출기에 투입해 압출성형으로 인증표준물질을 수득하는 과정이다. 여기서 상기 압출기의 운전조건은 마스터배치시료 제조과정과 동일하게 인증표준물질용 시료혼합물을 10 kg/hr로 투입하고, 190 ℃에서 압출성형하여 인증표준물질을 수득한다. 또한, 상기 인증표준물질의 균질성을 향상시키기 위해 압축성형을 2~5회 반복수행할 수 있다.
The certification standard material molding process is a process of obtaining a certification standard material by extrusion molding by mixing the master batch sample and the high-impact polystyrene material mixture mixed in the manufacturing process of the sample mixture for the certification standard material into the extruder. Here, the operating conditions of the extruder is a sample mixture for the authentication standard material at 10 kg / hr in the same manner as the production process of the master batch sample, and extrusion molding at 190 ℃ to obtain a certified standard material. In addition, compression molding may be repeated 2 to 5 times to improve the homogeneity of the certified standard material.
한편, 도 2를 참조한 바와 같이 상기 인증표준물질성형과정에서 제조된 인증표준물질은 시료전처리법과 동위원소희석질량분석법에 의해 균질성, 안정성, 인증값의 불확도산출하여 적합성여부를 판단하는 검증과정을 거쳐 제조된 인증표준물질 중 난연제 들의 기준값(인증값)을 최종 적으로 인증한다.Meanwhile, as shown in FIG. 2, the certified standard material manufactured in the process of forming the certified standard material is subjected to a verification process of determining the suitability by calculating the uncertainty of homogeneity, stability, and certified value by sample pretreatment and isotope dilution mass spectrometry. Finally, the standard value (certification value) of flame retardants among certified standard materials is certified.
상기 검증과정에서는 펠렛형태의 인증표준물질을 분쇄하여 시료를 준비하고, 준비된 시료에는 시료에 포함된 측정하고자 하는 난연제들과 동위원소비가 1:1 이 되도록 동위원소화합물을 가하여 가한 동위원소화합물들이 시료의 매트릭스와 상호 작용하는 현상을 화학적 또는 물리적으로 평형이 이루어지도록 하는 동위원소화합물 첨가단계가 수행된다.In the verification process, a sample is prepared by pulverizing a certification standard material in pellet form, and isotopic compounds added to the prepared sample by adding an isotope compound so that the isotope ratio is 1: 1 with the flame retardants included in the sample are measured. An isotope addition step is performed to chemically or physically equilibrate the interaction with the matrix of the sample.
상기 동위원소화합물 첨가단계 다음으로는 동위원소화합물이 첨가된 시료를 toluene/THF에 녹인후 메탄올을 가해 플라스틱매질을 석출하여 여과시키는 단계가 수행된다.After the isotope compound addition step, a sample in which the isotope compound is added is dissolved in toluene / THF, and methanol is added to precipitate and filter the plastic medium.
상기 여과된 용액에는 질소가스를 공급하여 용매인 toluene/THF와 메탄올을 휘발시키는 용매제거단계가 수행된다.The solvent is removed by supplying nitrogen gas to the filtered solution to volatilize the solvent, toluene / THF and methanol.
상기 용매가 휘발되고 남은 성분에는 톨루엔을 첨가하여 남은 성분을 녹인 후 여과를 통해 이물질을 제거하여 분석시료를 준비하는 단계가 이루어진다.After the solvent is volatilized, toluene is added to the remaining components to dissolve the remaining components and to remove foreign substances through filtration to prepare an analytical sample.
상기 단계에서 준비된 분석시료와 그 분석시료 중에 포함된 난연제의 농도와 비슷한 농도범위로 각각의 순수 난연제 및 난연제치환용 동위원소화합물들을 혼합하여 준비한 검정용 혼합표준용액을 각각 GC/MS 분석기에 주입하여 지시하는 감응값을 비교하므로써 인증표준물질시료 중 각 난연제의 농도를 정확히 분석하는 단계가 수행된다.
Inject the assay mixed standard solution prepared by mixing each pure flame retardant and the flame retardant substituted isotope compound in the concentration range similar to the concentration of the flame retardant included in the analyte sample and the sample to the GC / MS analyzer, respectively. An accurate analysis of the concentration of each flame retardant in the certified reference material sample is performed by comparing the indicated response values.
여기서 상기 동위원소화합물 첨가단계에서의 펠렛형태의 인증표준물질은 다량 제조된 것 중 무작위로 다수 선택해 각각 분석하고 이의 분석값을 서로 대비하여 유사한지를 판단해 균질성을 검증하도록 한다.Here, the authentication standard material in the form of pellets in the step of adding the isotope compound is randomly selected from among a large number of manufactured ones and analyzed, respectively, and the analysis values thereof are compared with each other to determine homogeneity.
또한, 균질성이 확인된 인증표준물질은 동일한 시점에서 제조된 것 중 제조 즉시 또는 1 ~ 12개월 보관한 다음 분석하여 시간에 따른 성분변화의 안정성을 검증하도록 할 수 있다.In addition, the certified standard material confirmed homogeneity can be stored at the same time or immediately after the manufacture or stored for 1 to 12 months and then analyzed to verify the stability of the component change over time.
아울러 상기 균질성검증과 안정성 검증에서의 결과를 이용하여 인증값에 대한 불확도산출에 반영하여 평가할 수 있다.In addition, the results from the homogeneity verification and stability verification can be used to evaluate the uncertainty calculation for the authentication value.
불확도의 산출방법은 인증표준물질 중 난연제의 농도를 구하는 수학식1로부터 각 입력값들의 불확도를 표1과 같이 불확도 요인으로 구하고 그 불확도요인들을 합산하여 인증표준물질 중 난연제들의 인증값에 대한 불확도를 산출한다.The method of calculating the uncertainty is to calculate the uncertainty of the flame retardants in the certified standard material by calculating the uncertainty of each input value as the uncertainty factor as shown in Table 1 from the equation (1) which calculates the concentration of the flame retardant in the certified standard material, and adding the uncertainty factors. Calculate.
C : concentration of analyte (flame retardant) in sample (CRM sample)
시료(인증표준물질 시료)속에 포함된 분석대상 성분(난연제)의 농도 C : concentration of analyte (flame retardant) in sample (CRM sample)
Concentration of the analyte (flame retardant) contained in the sample (certified standard material sample)
Msample : weight of sample taken for analysis
분석을 위해 취한 시료 무게 M sample : weight of sample taken for analysis
Sample weight taken for analysis
Mis-sol,spiked : weight of isotope labeled standard solution spiked to sample taken for analysis
분석을 위해 취한 시료에 가한 동위원소치환 표준용액의 무게 M is-sol, spiked : weight of isotope labeled standard solution spiked to sample taken for analysis
Weight of isotopically substituted standard solution added to the sample taken for analysis
Cs-sol : concentration of stndard solution
표준용액의 농도 C s-sol : concentration of stndard solution
Standard solution concentration
Ms-sol, std : weight of standard solution added to STD Mix
표준물질 혼합용액을 제조하기 위해 가한(제조하는데 사용한) 표준용액의 무게 M s-sol, std : weight of standard solution added to STD Mix
Weight of the standard solution (used in the preparation) added to prepare a mixture of standards
Mis-sol,sptd : weight of isotope labeled standard solution added to STD Mix
표준물질 혼합용액을 제조하기 위해 가한(제조하는데 사용한) 동위원소치환 표준용액의 무게 M is-sol, sptd : weight of isotope labeled standard solution added to STD Mix
Weight of isotopically substituted standard solution (used to manufacture) added to prepare a mixture of standards
ARsample : Area ratio of the analyte to the isotope labeled analogue from GC/MS-SIM measurent of sample
가스크로마토그래피/질량분석기의 선택이온 모드에서 시료측정 시 측정한 분석대상성분과 그에 대등한 동위원소 치환물질의(그것과 동일한 성분에 동위원소가 치환된) 피크면적들의 비율 AR sample : Area ratio of the analyte to the isotope labeled analogue from GC / MS-SIM measurent of sample
The ratio of the peak area of the analyte and its corresponding isotope-substituted material (with isotope substituted in the same component) measured in the sample measurement in the gas ion chromatography / mass spectrometer's selective ion mode.
ARstd : Area ratio of the analyte peak to the isotope labeled analogue from GC/MS-SIM measurent of STD Mix
가스크로마토그래피/질량분석기의 선택이온 모드에서 혼합표준용액 측정 시 측정한 분석대상성분과 그에 대등한 동위원소 치환물질의(그것과 동일한 성분에 동위원소가 치환된) 피크면적들의 비율
AR std : Area ratio of the analyte peak to the isotope labeled analogue from GC / MS-SIM measurent of STD Mix
The ratio of the peak area of the component to be analyzed and its isotope-substituted equivalents (isotope substituted in the same component) measured in the mixed standard solution in the gas ion chromatography / mass spectrometer's selective ion mode.
실시예1 - 인증표준물질 제조Example 1 Preparation of Certified Standards
냉동 분쇄된 고충격폴리스티렌 990 g 에 대해 난연제(polybrominated diphenyl ether, octa bromo diphenyl oxide (FR-1208), Dead Sea Bromine Co., Makleff House 12 Kroitzer St., P.O. Box 180 Beer Sheva 84101, Israel)를 10000 mg을 혼합하여 최종 제조되는 인증표준물질의 측정기준농도범위의 10배에 달하는 농도가 되도록 (10000 mg/kg, 1 %)이 되도록 혼합하였다.
Flame retardant (polybrominated diphenyl ether, octa bromo diphenyl oxide (FR-1208), Dead Sea Bromine Co.,
또한, 분산제인 칼슘스테아레이트와 난연조제인 삼산화 안티몬을 각각 5000 mg, 35000 mg을 칭량하여 혼합하였다.In addition, 5000 mg and 35000 mg of calcium stearate as a dispersant and antimony trioxide as a flame retardant were weighed and mixed respectively.
상기 혼합에는 con-mixer를 사용하였고 20분 이상 혼합이 이루어지도록 하여 혼합시료를 제조하였다.A con-mixer was used for the mixing and a mixed sample was prepared by mixing for 20 minutes or more.
상기 혼합시료를 압출기의 주입장치를 통해 10 kg/hr로 투입하고, 190 oC에서 압출 성형하여 펠렛 형태의 마스터배치시료를 제조하였다. 여기서 상기 마스터배치시료는 압출기로 2회 반복투입하여 균질하게 하였다.The mixed sample was introduced at 10 kg / hr through an injection device of an extruder, and extruded at 190 ° C. to prepare a master batch sample in pellet form. Here, the master batch sample was added to the extruder twice and homogenized.
제조할 인증표준물질의 난연제 측정기준농도에 맞게 마스터배치시료와 펠렛형태의 고충격폴리스티렌소재를 각각 칭량한 후 혼합기에서 30분 이상 혼합하여 인증표준물질용시료혼합물을 제조하였다. 이 때 상기 마스터배치시료와 고충격폴리스티렌소재의 혼합은 측정기준농도의 10배에 해당하는 농도를 가지는 마스터배치시료 1 kg에 대해 고충격폴리스티렌 소재 9 kg을 혼합하여 난연제 농도를 희석하여 측정기준농도를 갖도록 설정한다.Sample batches for certified reference materials were prepared by weighing a masterbatch sample and pellet-type high-impact polystyrene material, respectively, in accordance with the flame retardant measurement standard concentration of the certified standard material to be prepared and mixing in a mixer for at least 30 minutes. At this time, the mixture of the master batch sample and the high impact polystyrene material is mixed with 9 kg of high impact polystyrene material to 1 kg of the master batch sample having a concentration corresponding to 10 times the concentration of the reference standard concentration by diluting the flame retardant concentration Set to have.
상기 인증표준물질용시료혼합물은 압출기의 주입장치를 통해 10 kg/hr로 투입하고, 190 oC에서 3회 반복 압출성형 하여 균질한 인증표준물질을 제조하였다.
The sample mixture for the certified standard material was introduced at 10 kg / hr through an injection device of an extruder, and was repeatedly extruded three times at 190 ° C. to produce a homogeneous certified standard material.
실시예2 - 인증표준물질의 검증Example 2 Verification of Certified Standards
실시예1에서 제조된 난연제 성분들을 포함하는 고충격폴리스티렌 인증표준물질을 기 확립된 시료전처리법과 동위원소희석질량분석법을 이용한 난연제 측정방법을 통해 그 유효성을 확인하여 도 3에 나타내었다. The high-impact polystyrene-certified standard material containing the flame retardant components prepared in Example 1 was confirmed by the flame retardant measurement method using a pre-established sample pretreatment method and isotope dilution mass spectrometry, and is shown in FIG. 3.
이때 균질성 평가를 위한 시료로는 제조한 후 갈색병에 10 g 씩 포장하여 보관 중인 1000개의 고충격폴리스티렌 인증표준물질 중에서 12개 이상을 무작위로 선택하였다. 도 3를 참조한 바와같이 무작위로 선택된 각 시료(인증표준물질)은 거의 균질한 성분을 갖고 있음을 알 수 있다.
At this time, as a sample for homogeneity evaluation, 12 or more randomly selected from 1000 high-impact polystyrene certified standards stored in 10 g of brown bottles after storage were prepared. As shown in Figure 3 it can be seen that each sample randomly selected (certified standard material) has a nearly homogeneous component.
상기 시료전처리법과 동위원소희석질량분석법은 아래 방법에 의해 실시하였다.The sample pretreatment method and the isotope dilution mass spectrometry were performed by the following method.
-시료의 채취 및 분쇄Sample Collection and Grinding
전체 시료를 대표할 수 있는 플라스틱 시료를 채취한 후 사전에 3 mm 이하의 크기로 잘라 잘 혼합한다. 다시 이 시료 10 g 당 1 g 이상을 무작위로 취하여 0.5 mm 이하의 크기로 분쇄한 후 head space가 작은 갈색병에 넣고 잘 흔들어 섞는다. 이 시료를 소형 알미늄 컵을 사용하여 50 mg 이상 정확히 질량을 측정하고 기록한 후 20 mL 바이알에 넣는다. Take a plastic sample that can represent the entire sample, and cut it into 3 mm or less beforehand and mix well. Again, at least 1 g per 10 g of this sample is randomly pulverized to a size of 0.5 mm or less and placed in a brown bottle with a small head space. Accurately weigh and record this sample using a small aluminum cup at least 50 mg and place in a 20 mL vial.
-동위원소 치환물질 첨가Isotope substitution
동위원소비가 약 1:1 이 되는데 필요한 각 난연제들의 동위원소 물질의 양을 결정하고 0.25 ∼ 0.5 mL gas tight 시린지를 사용하여 전후 질량차를 정확히 측정하는 방법으로 20 mL 바이알속에 있는 시료에 가한다. Determine the amount of isotope of each flame retardant required for the isotope ratio to be about 1: 1 and add it to the sample in the 20 mL vial by accurately measuring the mass difference before and after using a 0.25 to 0.5 mL gas tight syringe. .
이 때 주사기로 미리 동위원소치환난연제용액 일정량을 취한다. 주사기의 plunger를 약간 더 잡아당겨 주사기 끝 부분에 공기가 들어가게 한 후 작은 silicon septum을 주사기 바늘 끝에 꽂아 용매의 휘발을 막는다. 이 주사기의 무게를 측정한 후 septum을 빼고 동위원소치환 난연제물질용액을 시료 용기에 투입한다. 다시 septum을 꽂고 주사기의 무게를 측정한다. 표준용액 투입 전후의 주사기 무게의 차이로부터 시료에 투입된 동위원소치환난연제용액의 질량을 산출한다. At this time, take a predetermined amount of isotopically substituted flame retardant solution with a syringe. Pull the syringe's plunger slightly further to allow air to enter the tip of the syringe, and then place a small silicon septum on the tip of the syringe needle to prevent volatilization of the solvent. After weighing the syringe, remove the septum and place the isotopically substituted flame retardant solution into the sample container. Insert the septum again and weigh the syringe. The mass of the isotopically substituted flame retardant solution added to the sample is calculated from the difference in the weight of the syringe before and after adding the standard solution.
분석대상 난연제는 The flame retardant to be analyzed
BDE154 : 2,2',4,4',5,6'-Hexabromodiphenyl ehter: m/z 643.5310BDE154: 2,2 ', 4,4', 5,6'-Hexabromodiphenyl ehter: m / z 643.5310
BDE183 : 2,2',3,4,4',5',6-Heptabromodiphenyl ehter: m/z 721.4220BDE183: 2,2 ', 3,4,4', 5 ', 6-Heptabromodiphenyl ehter: m / z 721.4220
BDE203 : 2,2',3,4,4,',5,5',6-Octabromodiphenyl ehter: m/z 801.3500BDE203: 2,2 ', 3,4,4,', 5,5 ', 6-Octabromodiphenyl ehter: m / z 801.3500
BDE206 : 2,2',3,3',4,4',5,5',6-Nonabromodiphenyl ehter: m/z 719.2610BDE206: 2,2 ', 3,3', 4,4 ', 5,5', 6-Nonabromodiphenyl ehter: m / z 719.2610
BDE209 : Decabromodiphenyl ehter: m/z 799.170 이고, BDE209: Decabromodiphenyl ehter: m / z 799.170,
동위원소치환 난연제는 Isotope substitution flame retardant
13C12-2,2',4,4',5,6'-Hexabromodiphenyl ehter: m/z 655.5730 13 C 12 -2,2 ', 4,4', 5,6'-Hexabromodiphenyl ehter: m / z 655.5730
13C12-2,2',3,4,4',5',6-Heptabromodiphenyl ehter: m/z 733.4840 13 C 12 -2,2 ', 3,4,4', 5 ', 6-Heptabromodiphenyl ehter: m / z 733.4840
13C12-2,2',3,3',4,4,',6,6'-Octabromodiphenyl ehter: m/z 813.3920 13 C 12 -2,2 ', 3,3', 4,4, ', 6,6'-Octabromodiphenyl ehter: m / z 813.3920
13C12-2,2',3,3',4,4',5,5',6-Nonabromodiphenyl ehter: m/z 731.3030 13
13C12-Decabromodiphenyl ehter: m/z 811.2110 로 이루어졌다. 13 C 12 -Decabromodiphenyl ehter: m / z 811.2110.
-추출 및 전처리Extraction and Pretreatment
본 시험에서는 시료를 toluene/THF (1:1 v/v)에 녹인 후 메탄올을 가해 플라스틱 매질을 석출시고 여과해 제거하는 방법을 사용한다. 시료가 담긴 20 mL 바이알에 toluene/THF (1:1 v/v)을 시료 50 ∼ 200 mg 당 6 mL를 넣고 10분간 초음파추출기를 사용하여 녹인 후 완전히 녹을 때까지 세게 혼합한다. Toluene/THF (1:1 v/v) 6 mL 당 Methanol 7 mL를 넣고 석출시킨 후 아주 천천히 아래위로 병을 2번 정도 뒤집어 혼합한다. 1회용 실린지 필터(PVDF 25 mm, 0.45 ㎛, Whatman)를 이용하여 50 mL TurboVap용 튜브에 여과한다.In this test, the sample is dissolved in toluene / THF (1: 1 v / v), and methanol is added to precipitate the plastic medium, which is filtered off. Toluene / THF (1: 1 v / v) is added to 50 mL to 200 mL of sample, 6 mL per 50 mg to 200 mg of sample is dissolved using an ultrasonic extractor for 10 minutes, and mixed until melted completely. Add 7 mL of Methanol per 6 mL of toluene / THF (1: 1 v / v), precipitate, and mix the bottle upside down two times very slowly. Filter into a 50 mL TurboVap tube using a disposable syringe filter (PVDF 25 mm, 0.45 μm, Whatman).
약 45 ℃에서 질소 가스를 불어 용매를 완전히 휘발시킨다. Toluene 0.7 mL를 첨가하여 50 mL 튜브 내벽 주위를 잘 세척하여 녹인 후 준비된 여과 시린지에 넣고 다시 toluene 0.3 mL로 동일하게 세척 후 여과시린지에 넣어 여과 (PTEF 13 mm, 0.2 ㎛, Whatman)한다. 갈색 자동시료주입기용 바이알에 담아 분석한다.
Nitrogen gas is blown at about 45 ° C. to evaporate the solvent completely. 0.7 mL of toluene is added to wash the inner wall of the 50 mL tube, and then dissolved. Put it in the prepared filtration syringe and wash the same with 0.3 mL of toluene, and then put it in the filtration syringe (PTEF 13 mm, 0.2 μm, Whatman). Analyze in a brown autosampler vial.
-GC/MS분석GC / MS analysis
준비된 GC/MS 자동시료주입기 트레이에 혼합표준용액과 시료를 장착한다. 상기 독립적으로 제조하여 검증을 거쳐 선택한 한 종의 혼합표준용액 바이알 다음에 시료들을 놓고 시료의 개수가 많은 경우 시료 사이 적절한 간격으로 혼합표준용액을 넣고 분석한다 (시료 4개 다음에 동일한 혼합표준용액을 분석한다). 첫 번째 바이알부터 마지막 바이알까지 한번씩 분석하고 다시 이 과정을 정해진 횟수 (3번 이상) 반복한다. Load the mixed standard solution and sample in the prepared GC / MS autosampler tray. Samples are prepared after the above-mentioned one independently prepared and validated mixed standard solution vial, and if the number of samples is large, the mixed standard solution is analyzed at appropriate intervals between the samples (four samples followed by the same mixed standard solution). Analyze). Analyze once from the first vial to the last vial and repeat this process a specified number of times (at least three times).
측정조건 1) 전자 이온화법: 일반적으로 70 eV, 300 μA 조건 사용. 기기 상황에 따라 변경 가능 2) Detector: 1.2 kV x 1/16 x 1 기기 상황에 따라 변경 가능 3) Selected m/z for SIM mode:
Measuring conditions 1) Electron ionization: generally 70 eV, 300 μA. 2) Detector: 1.2 kV x 1/16 x 1 Can be changed according to the device 3) Selected m / z for SIM mode:
한편, 균일성이 검증된 인증표준물질을 이용한 안정도는 시료 3개 이상을 무작위로 취하여 위의 동위원소희석질량분석법에 의해 각 난연제들의 측정한 결과를 바탕으로 11개월간 안정도를 평가하고 그 결과를 하기 표2에 나타내었고, 이는 인증값들의 불확도 산출에 반영하였다. On the other hand, the stability using the certified standard material, which has been verified for uniformity, takes three or more samples at random and evaluates the stability for 11 months based on the measurement results of the respective flame retardants by the isotope dilution mass spectrometry. It is shown in Table 2, which is reflected in the calculation of the uncertainty of the authentication values.
참고한 바와같이 시간에 따른 물질성분변화가 없음을 알 수 있으며, 표준편차도 대부분 0.2~1.2의 범위를 갖고 있어 물질이 안정도가 우수함을 알 수 있다.
As can be seen that there is no change in the composition of the material over time, and the standard deviation also has a range of 0.2 ~ 1.2, indicating that the material has excellent stability.
상기 균질도와 안정도가 확인된 인증표준물질 소재는 기확립된 시료전처리법과 고충격폴리스티렌 중 난연제 측정을 위한 동위원소희석질량분석법을 사용하여 각 난연제 성분의 인증값 및 불확도를 산출하였다. The certified standard material having homogeneity and stability was calculated using the pre-established sample pretreatment method and isotope dilution mass spectrometry for flame retardant measurement in high impact polystyrene to calculate the certification value and uncertainty of each flame retardant component.
이를 위해 분석하려는 인증표준물질 시료에 알고 있는 양의 각 성분별 동위원소치환 물질을 첨가하고 전처리 과정을 거친 후 GC/MS를 사용하여 시료중의 동위원소비를 측정하므로 써 시료 중 분석대상 성분의 농도를 계산하였고, 이를 하기 표 3에 나타내었다. To this end, add isotopically substituted substances of each component to the certified standard sample to be analyzed, and after pretreatment, measure the isotope ratio in the sample using GC / MS. The concentration was calculated and shown in Table 3 below.
상기 "a)PBDE congeners are numbered according to IUPAC schemes."는
"PBDE류의 동족체들은 국제 순수·응용화학 연합(International Union of Pure and Applied Chemistry, IUPAC)의 명명법에 따라 번호를 부여하였음."을 의미함.
상기 "b)The numbers following "±" are the expanded uncertainties of the preceding values, estimated in accordance with the ISO Guide to the Expression of Uncertainty in measurment (GUM) with a coverage factor k = 2, corresponding to a level of confidence of about 95%."는
" "±"부호 다음의 숫자는 부호 앞에 표시된 값들의 확장불확도로서 ISO에서 제정한 측정 불확도 표시 가이드에 따라 95% 신뢰수준에서 포함인자(k) 2로 추정된 값이다." 를 의미함.
"A) PBDE congeners are numbered according to IUPAC schemes."
"PBDE homologs are numbered according to the nomenclature of the International Union of Pure and Applied Chemistry (IUPAC)."
Above "b) The numbers following" ± "are the expanded uncertainties of the preceding values, estimated in accordance with the ISO Guide to the Expression of Uncertainty in measurment (GUM) with a coverage factor k = 2, corresponding to a level of confidence of about 95%. "
"The number following the" ± "sign is the extended uncertainty of the values indicated before the sign, which is an estimate of inclusion factor ( k ) 2 at the 95% confidence level in accordance with the ISO measurement guide for measurement uncertainty." Means.
표 3에서의 "±"이후 숫자는 불확도를 나타낸 것이며, 불확도계산에서의 보상벡터는 k=2로 하여 95%의 신뢰도를 갖음을 알 수 있다. The number after "±" in Table 3 represents the uncertainty, and it can be seen that the compensation vector in the uncertainty calculation has a reliability of 95% by k = 2.
따라서, 상기 0.1 % 농도 범위의 난연제 성분들을 포함하는 균질하고 11개월간 안정한 인증표준물질을 제조하고 이의 성분함량을 정확하게 인증하여 난연제성분 측정용 물질로의 사용에 적합함을 알 수 있다.
Accordingly, it can be seen that a homogeneous 11 months stable certification standard material including the flame retardant components in the 0.1% concentration range is prepared and its component content is accurately certified to be suitable for use as a material for measuring flame retardant components.
Claims (10)
고충격폴리스티렌과 난연제 또는 난연제혼합물을 칭량하여 혼합해 혼합시료를 제조하되, 상기 혼합시료의 난연제 농도를 측정기준농도의 10배에 해당하는 농도로 설정하는 마스터배치시료 난연제농도 설정과정과;
상기 혼합시료를 압출기로 투입하여 펠렛형태로 압출성형하고 이를 2~5회 반복하여 균질한 마스터배치시료를 제조하는 마스터배치시료 제조과정과;
상기 마스터배치시료를 칭량하고, 칭량된 마스터배치시료의 난연제성분 농도가 인증표준물질의 측정기준농도와 같아지도록 펠렛형태의 고충격폴리스티렌 소재를 칭량하여 혼합하는 인증표준물질용시료혼합물 제조과정과;
상기 인증표준물질용시료혼합물을 압출기에 투입하여 2~5회 압출성형하여 인증표준물질을 제조하는 인증표준물질성형과정;을 포함하여 이루어지는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.In the high impact polystyrene certified standard material manufacturing method for accurately measuring the flame retardant component contained in the high impact polystyrene material,
Preparing a mixed sample by weighing and mixing a high impact polystyrene and a flame retardant or a flame retardant mixture, and setting a flame retardant concentration of the master batch sample to set the flame retardant concentration of the mixed sample to a concentration corresponding to 10 times the reference concentration;
A process for producing a master batch sample by inserting the mixed sample into an extruder and extruding it into pellets to produce a homogeneous master batch sample by repeating it 2 to 5 times;
Preparing a sample mixture for a certification standard material by weighing the master batch sample and weighing and mixing a high impact polystyrene material in pellet form such that the flame retardant component concentration of the weighed master batch sample is equal to the measurement standard concentration of the certified standard material;
Method for manufacturing a high-impact polystyrene certified standard material for flame retardant measurement, characterized in that it comprises a; certification standard material molding process for producing a certified standard material by inserting the sample mixture for the certified standard material into an extruder 2 to 5 times. .
상기 인증표준물질성형과정에서 제조된 인증표준물질은 시료전처리법과 동위원소희석질량분석법에 의해 균질성, 안정성, 인증값의 불확도산출하여 적합성여부를 판단하는 검증과정이 더 이루어지는 것을 특징을 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method of claim 1,
The certified standard material manufactured in the process of forming the certified standard material is a flame retardant for measuring flame retardant, characterized in that a verification process is performed to determine the suitability by calculating the uncertainty of homogeneity, stability, and certified value by sample pretreatment and isotope dilution mass spectrometry. High impact polystyrene certified standard material manufacturing method.
상기 난연제농도설정과정에서의 혼합시료에는 분산제와, 난연조제가 더 혼합되는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method of claim 1,
The method of manufacturing a high impact polystyrene certified standard material for measuring a flame retardant, characterized in that the mixed sample in the flame retardant concentration setting process is further mixed with a dispersant and a flame retardant aid.
상기 혼합시료의 혼합은 난연제 100~10000 mg에 고충격폴리스티렌을 잔량으로 혼합한 혼합시료 1 kg에 대해 분산제 4000~6000 mg, 난연조제 30000~40000 mg 이 혼합되는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법. The method of claim 3,
Mixing of the mixed sample is a high impact for measuring the flame retardant, characterized in that the dispersant 4000 ~ 6000 mg, flame retardant aid 30000 ~ 40000 mg is mixed with respect to 1 kg of the mixed sample of the flame retardant 100 ~ 10000 mg mixed with high impact polystyrene in the remaining amount Polystyrene Certified Standards
상기 마스터배치시료제조과정과 인증표준물질성형과정에서의 압출기는 190 ℃, 10 kg/hr 로 압출성형이 이루어지는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method of claim 1,
The extruder in the master batch sample manufacturing process and the certification standard material molding process 190 ℃, 10 kg / hr extrusion molding is characterized in that the high impact polystyrene certified standard material manufacturing method for measuring the flame retardant.
상기 검증과정에서는
펠렛형태의 인증표준물질을 분쇄하여 시료를 준비하고, 준비된 시료의 난연제들과 동위원소비가 1:1이 되도록 동위원소화합물을 가하여 치환이 이루어지도록 하는 동위원소화합물 첨가단계와;
동위원소화합물이 첨가된 시료를 toluene/THF에 녹인후 메탄올을 가해 플라스틱매질을 석출하여 여과시키는 단계와;
여과된 용액에 질소가스를 공급하여 용매인 toluene/THF와 메탄올을 휘발시키는 용매제거단계와;
상기 용매가 휘발되고 남은 고체성분에 톨루엔을 첨가하여 녹인 후 여과를 통해 이물질을 제거하여 분석시료를 준비하는 단계와;
상기 분석시료와, 측정기준농도로 순수 난연제와 동위원소화합물을 혼합한 혼합표준용액을 GC/MS 분석기에 투입하여 분석하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method of claim 2,
In the verification process
Isotope compound addition step of preparing a sample by grinding the certified standard material of the pellet form, adding the isotope compound so that the isotope ratio is 1: 1 with the flame retardant of the prepared sample to be replaced;
Dissolving the sample to which the isotope compound is added in toluene / THF, and then adding methanol to precipitate and filter the plastic medium;
A solvent removing step of supplying nitrogen gas to the filtered solution to volatilize the solvent, toluene / THF and methanol;
Preparing an analytical sample by dissolving the solvent by adding toluene to the remaining solid component and removing foreign substances through filtration;
The analysis sample and the mixed standard solution mixed with a pure flame retardant and an isotope compound at a measurement reference concentration to a GC / MS analyzer for analysis; high impact polystyrene certified standard material for measuring the flame retardant comprising a Manufacturing method.
상기 동위원소화합물 첨가단계에서의 펠렛형태의 인증표준물질은 다량 제조된 것 중 무작위로 다수선택해 각각 분석하여 분석값을 대비하여 균질성을 검증하도록 한 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method according to claim 6,
Pellet-type certified standard material in the step of adding the isotope compound is selected from a large number of randomly prepared high-impact polystyrene certified standard material for flame retardant measurement, characterized in that to verify the homogeneity against the analysis value by analyzing each of the randomly selected Manufacturing method.
상기 동위원소화합물 첨가단계에서의 펠렛형태의 인증표준물질은 동일한 시점에서 제조된 것 중 제조 즉시와 1 ~ 12개월 보관한 다음 분석하여 시간에 따른 성분변화의 안정성을 검증하도록 한 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.The method of claim 7, wherein
The standard material of pellet form in the step of adding the isotope compound was prepared at the same time and stored for 1 to 12 months immediately after analysis, and then analyzed to verify the stability of the component change over time. Method for manufacturing high impact polystyrene certified standards for measurement.
상기 동위원소화합물 첨가단계에서의 펠렛형태의 인증표준물질은 인증표준물질 중 난연제의 농도를 구하는 하기 수학식 1에 포함된 각 입력값들의 불확도를 표 1의 불확도요인으로 구하고, 그 불확도요인들을 합산하여 인증표준물질 중 난연제들의 인증값에 대한 불확도를 산출하는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질 제조방법.
[수학식 1]
C : concentration of analyte (flame retardant) in sample (CRM sample)
시료(인증표준물질 시료)속에 포함된 분석대상 성분(난연제)의 농도
Msample : weight of sample taken for analysis
분석을 위해 취한 시료 무게
Mis-sol,spiked : weight of isotope labeled standard solution spiked to sample taken for analysis
분석을 위해 취한 시료에 가한 동위원소치환 표준용액의 무게
Cs-sol : concentration of stndard solution
표준용액의 농도
Ms-sol, std : weight of standard solution added to STD Mix
표준물질 혼합용액을 제조하기 위해 가한(제조하는데 사용한) 표준용액의 무게
Mis-sol,sptd : weight of isotope labeled standard solution added to STD Mix
표준물질 혼합용액을 제조하기 위해 가한(제조하는데 사용한) 동위원소치환 표준용액의 무게
ARsample : Area ratio of the analyte to the isotope labeled analogue from GC/MS-SIM measurent of sample
가스크로마토그래피/질량분석기의 선택이온 모드에서 시료측정 시 측정한 분석대상성분과 그에 대등한 동위원소 치환물질의(그것과 동일한 성분에 동위원소가 치환된) 피크면적들의 비율
ARstd : Area ratio of the analyte peak to the isotope labeled analogue from GC/MS-SIM measurent of STD Mix
가스크로마토그래피/질량분석기의 선택이온 모드에서 혼합표준용액 측정 시 측정한 분석대상성분과 그에 대등한 동위원소 치환물질의(그것과 동일한 성분에 동위원소가 치환된) 피크면적들의 비율
[표 1]
9. The method of claim 8,
The pellet-type certified standard material in the step of adding the isotope compound obtains the uncertainty of each input value included in Equation 1 below to obtain the concentration of the flame retardant among the certified standard materials as the uncertainty factors in Table 1, and adds the uncertainty factors. Method for producing a high-impact polystyrene certified standard material for flame retardant measurement, characterized in that for calculating the uncertainty of the certification value of the flame retardant among the certified standard material.
[Equation 1]
C : concentration of analyte (flame retardant) in sample (CRM sample)
Concentration of the analyte (flame retardant) contained in the sample (certified standard material sample)
M sample : weight of sample taken for analysis
Sample weight taken for analysis
M is-sol, spiked : weight of isotope labeled standard solution spiked to sample taken for analysis
Weight of isotopically substituted standard solution added to the sample taken for analysis
C s-sol : concentration of stndard solution
Concentration of Standard Solution
M s-sol, std : weight of standard solution added to STD Mix
Weight of the standard solution (used in the preparation) added to prepare a mixture of standards
M is-sol, sptd : weight of isotope labeled standard solution added to STD Mix
Weight of isotopically substituted standard solution (used to manufacture) added to prepare a mixture of standards
AR sample : Area ratio of the analyte to the isotope labeled analogue from GC / MS-SIM measurent of sample
The ratio of the peak area of the analyte and its corresponding isotope-substituted material (with isotope substituted in the same component) measured in the sample measurement in the gas ion chromatography / mass spectrometer's selective ion mode.
AR std : Area ratio of the analyte peak to the isotope labeled analogue from GC / MS-SIM measurent of STD Mix
The ratio of the peak area of the component to be analyzed and its isotope-substituted equivalents (isotope substituted in the same component) measured in the mixed standard solution in the gas ion chromatography / mass spectrometer's selective ion mode.
[Table 1]
난연제 10~1000 mg과 잔량으로 고충격폴리스티렌 혼합된 혼합시료 1 kg에 대해 분산제 4000~6000 mg, 난연조제 30000~40000 mg가 균일하게 혼합되어 펠럿형태를 갖는 것을 특징으로 하는 난연제 측정용 고충격폴리스티렌 인증표준물질.In the high impact polystyrene certified standard material used to accurately measure the flame retardant component contained in the high impact polystyrene material,
High-impact polystyrene for flame retardant measurement, characterized in that the flame retardant 10 ~ 1000 mg and the remaining amount of the high impact polystyrene mixed sample 1 kg mixed dispersant 4000 ~ 6000 mg, flame retardant aid 30000 ~ 40000 mg uniformly mixed Certified Standards.
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| CN115236226A (en) * | 2022-07-14 | 2022-10-25 | 杭州希科检测技术有限公司 | Method for determining vinyl-tri (2-methoxyethoxy) silane in electronic and electric products |
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