WO2023035293A1 - 一种涂料制品中丙烯酰胺的测定方法 - Google Patents

一种涂料制品中丙烯酰胺的测定方法 Download PDF

Info

Publication number
WO2023035293A1
WO2023035293A1 PCT/CN2021/118390 CN2021118390W WO2023035293A1 WO 2023035293 A1 WO2023035293 A1 WO 2023035293A1 CN 2021118390 W CN2021118390 W CN 2021118390W WO 2023035293 A1 WO2023035293 A1 WO 2023035293A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylamide
extract
solution
treatment
paint
Prior art date
Application number
PCT/CN2021/118390
Other languages
English (en)
French (fr)
Inventor
陈昭晶
刘朋
孙慧玲
程婷婷
高冠军
黄德毅
李克香
薛洁
李倩
马占魁
王腾
张政超
Original Assignee
山东省环境保护科学研究设计院有限公司
山东省环科院环境检测有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东省环境保护科学研究设计院有限公司, 山东省环科院环境检测有限公司 filed Critical 山东省环境保护科学研究设计院有限公司
Publication of WO2023035293A1 publication Critical patent/WO2023035293A1/zh

Links

Images

Classifications

    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/14—Preparation by elimination of some components
    • 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
    • G01N30/64—Electrical detectors
    • G01N30/70—Electron capture detectors
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material
    • 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
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/067—Preparation by reaction, e.g. derivatising the sample

Definitions

  • the invention belongs to the technical field of analysis and detection, in particular to a method for measuring acrylamide in paint products.
  • Acrylamide has neurotoxicity, reproductive toxicity, developmental toxicity, genotoxicity and teratogenicity, etc.
  • the International Agency for Research on Cancer (IARC) lists acrylamide as a Class 2 carcinogen, that is, a possible human carcinogen. All countries in the world have listed acrylamide as a hazardous chemical.
  • Acrylamide is widely used in synthetic industries such as coatings and dyes. When acrylamide enters the environment, it can enter the human body through various channels such as the digestive tract, respiratory tract, skin and mucous membranes, etc., causing great harm to the environment and human health.
  • the gas chromatography-mass spectrometry detection of acrylamide has a relatively high detection limit; the liquid chromatography-tandem mass spectrometry instrument is expensive, the cost is high, and it is difficult to popularize; the sample matrix of coatings and its products is usually complex, with many impurities, and there is no literature yet.
  • the invention discloses a method for measuring acrylamide in paint products, comprising the following steps:
  • the pulverized paint product is extracted with a first extractant to obtain a first extract;
  • the first extract is subjected to bromination derivatization treatment, debromination treatment and centrifugation treatment in sequence, and the supernatant is taken;
  • the supernatant is extracted with a second extractant to obtain a second extract
  • the first extractant is an acetic acid solution with a mass fraction of 0.1%.
  • Potassium bromide and bromine water were sequentially added to the above-mentioned first extract after adjusting the pH value, mixed uniformly, and reacted for 1 h at 0-2° C. in the dark.
  • the bromine removal agent used in the bromine removal treatment is sodium sulfite.
  • the conditions of the centrifugation treatment are a rotating speed of 3000r/min and a time of 1-2min.
  • the second extractant is n-hexane: ethyl acetate mixed solution with a volume ratio of 4:1.
  • Concentrate the second extract add n-hexane for secondary concentration, transfer the secondary concentrate to a separatory funnel, add concentrated sulfuric acid to the separatory funnel while shaking until the second extract is colorless and clear , discard the lower concentrated sulfuric acid after standing for stratification;
  • the eluent used in the purification and concentration treatment is a mixed solution of n-hexane:ethyl acetate with a volume ratio of 9:1.
  • the fillers of the purification column are anhydrous sodium sulfate, basic silica gel, neutral silica gel, acid silica gel and neutral silica gel from top to bottom.
  • the beneficial effect of the present invention is: 2,3-dibromopropionamide is generated through the bromination reaction of acrylamide, the polarity and solubility are changed, and the organic phase is collected, which is convenient for purification treatment and improves the recovery rate; By further purifying and concentrating, impurity peaks are reduced, and the detection limit is reduced; finally, the gas chromatograph with electron capture detector is used to measure, and 2,3-dibromopropionamide has a higher response value on the electron capture detector, and has Higher sensitivity.
  • Fig. 1 shows a standard curve diagram of acrylamide according to an embodiment of the present invention
  • Fig. 2 shows the chromatogram of the sample solution 1 to be tested according to the embodiment of the present invention.
  • the present invention proposes a method for measuring acrylamide in paint products, comprising the following steps:
  • paint products mainly include paints, architectural coatings, acrylic emulsions and solid wastes generated during their production processes, or waste residues of paints, architectural coatings, acrylic emulsions, etc.
  • the pulverizing operation steps described in the present invention are only one of them, and other common pulverizing methods can also be used to pulverize the paint products to obtain corresponding samples that meet the requirements.
  • the pulverized paint product is extracted with a first extractant to obtain a first extract
  • the first extractant is an acetic acid solution with a mass fraction of 0.1%. Pure water is usually used as the extraction agent in the current existing technical solutions, but the stability of the target acrylamide in water is relatively poor, so the present invention uses 0.1% acetic acid solution instead of pure water as the extraction agent to extract propylene in the coating product. Amides, thereby improving the stability of the target substance in the extract, thereby increasing the recovery rate.
  • sodium thiosulfate is commonly used to remove unreacted bromine, but a lot of impurity peaks will be interfered. Therefore, the present invention uses sodium sulfite as bromine removal agent.
  • Sodium sulfite is a very inert reagent to organic matter and will not affect organic matter. , can effectively reduce the impurity peak of the sample solution to be tested.
  • the supernatant is extracted with a second extractant to obtain a second extract
  • n-hexane: ethyl acetate as the second extractant to the separatory funnel, mix, shake and deflate, let stand to separate layers, repeat the extraction twice, combine the organic phases, A second extract is obtained.
  • the second extractant adopts n-hexane:ethyl acetate mixed solution with a volume ratio of 4:1, which can reduce the dissolution of ethyl acetate in water and improve the extraction effect compared with the existing one that only uses ethyl acetate as the extractant.
  • the packing of the purification column is anhydrous sodium sulfate, basic silica gel, neutral silica gel, acid silica gel and neutral silica gel from top to bottom.
  • Purification and concentration treatment can effectively remove impurities in the sample solution to be tested, reduce the interference of the sample matrix, and lower the detection limit.
  • the invention adopts a gas chromatograph equipped with an electron capture detector to measure the content of acrylamide in the sample solution to be tested.
  • the reagents and equipment used in the examples of the present invention are as follows.
  • n-Hexane pesticide residue grade
  • hydrochloric acid solution Measure 250mL of concentrated hydrochloric acid, slowly add it into a volumetric flask filled with an appropriate amount of pure water, and dilute to IL with water;
  • sodium sulfite solution weigh 50.4g of sodium sulfite, dissolve it in a small amount of water, and dilute to 100mL;
  • Anhydrous sodium sulfate burn at 400°C for 4 hours, put it into a ground glass bottle after cooling, and store it in a desiccator;
  • Concentration device rotary evaporator, or equipment with equivalent performance such as concentrator;
  • Magnetic stirrer (with magnetic stirring bar);
  • Iodine bottle 250mL;
  • Microsyringe 10 ⁇ L, 50 ⁇ L, 250 ⁇ L.
  • Chromatographic column DB-5 quartz capillary column (30m ⁇ 0.25mm ⁇ 0.25um) or equivalent column;
  • Carrier gas nitrogen, purity ⁇ 99.999%.
  • the paint product is the waste residue of acrylic emulsion produced by a paint company
  • the supernatant was transferred to a separatory funnel, and 25 mL of n-hexane:ethyl acetate mixed solution (volume ratio 4:1) was added to the separatory funnel as the second extraction agent, after mixing, shaking and degassing, the layers were left to stand, Repeat the extraction twice, combine the organic phases to obtain the second extract;
  • the extract was colorless and clear, allowed to stand for stratification, discard the concentrated sulfuric acid in the lower layer, add 10mL of saturated potassium carbonate solution, stand for stratification, keep the organic phase, concentrate to 2mL, and obtain the concentrated sample solution to be tested;
  • the packings are anhydrous sodium sulfate, basic silica gel, neutral silica gel, acid silica gel and neutral silica gel from top to bottom, and the masses are 4g, 2g, 3g, 8g and 3g respectively; Add 30mL of n-hexane, put it on the column for activation, discard this part of the washing liquid, then add the concentrated sample solution to be tested, elute with 80mL of n-hexane:ethyl acetate mixed solution (volume ratio is 9:1), and collect to Put it into a concentrator in a concentrator cup, and use nitrogen gas to adjust the volume to 1 mL to obtain the sample solution 1 to be tested, and put it into a gas chromatograph for determination.
  • Derivatize, purify and concentrate according to the preparation steps of paint products measure according to the recommended chromatographic conditions, take the content (x, ng) of acrylamide in the solution to be tested in the standard series as the abscissa, and the corresponding chromatographic peak response value (peak area y) is the ordinate, and the standard curve is drawn, as shown in Figure 1, and the specific data are shown in Table 1.
  • the concentration of acrylamide in paint products is calculated according to the following formula:
  • Wi Ci/Mi
  • Ci is the acrylamide content (ng) obtained from the standard curve
  • Mi is the sampling amount (g) of the paint product
  • Wi is the concentration ( ⁇ g/kg) of acrylamide in the paint product.
  • Diatomaceous earth (or quartz sand) is used instead of the actual paint product, and the other sample preparation steps are the same, and a blank experiment is carried out while testing the sample. After testing, no acrylamide was detected in the blank experiment.
  • the acrylamide scalding amount of sample 3, sample 4, and sample 5 are all 10ng
  • the acrylamide scalding amount of sample 6, sample 7, and sample 8 are all 100ng
  • the spiked sample solution 3, the spiked sample solution 4, the spiked sample solution 5, the spiked sample solution 6, the spiked sample solution 7 and the spiked sample solution 8 were prepared, and they were determined according to the above chromatographic conditions .
  • the average recovery of spiked sample solution 3, spiked sample solution 4 and spiked sample solution 5 was 75.1%, with a relative standard deviation of 0.4%.
  • the average recovery rate of the spiked sample solution 6, the spiked sample solution 7 and the spiked sample solution 8 was 78.4%, and the relative standard deviation was 2.0%.
  • the specific data are shown in Table 3.
  • the present invention is not limited thereto, and it can measure paint products and coatings on the market, such as paints, architectural coatings, acrylic emulsions, etc. or paints, architectural paints, etc. Residues from paints, acrylic emulsions, etc. Those skilled in the art can make comprehensive considerations based on the measurement principles of the present invention and actual application conditions, as long as the principles of the present invention can be realized.
  • a method for measuring acrylamide in paint products proposed in the present invention generates 2,3-dibromopropionamide through acrylamide bromination reaction, changes polarity and solubility, collects organic phase, facilitates purification treatment, and improves recovery rate; by further purifying and concentrating, reducing impurity peaks and reducing the detection limit; finally using a gas chromatograph with an electron capture detector to measure, 2,3-dibromopropionamide has a higher response value on the electron capture detector , with higher sensitivity.

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

一种涂料制品中丙烯酰胺的测定方法，包括以下步骤：将涂料制品粉碎；粉碎后的所述涂料制品用第一萃取剂萃取，得到第一萃取液；将所述第一萃取液依次进行溴化衍生处理、除溴处理和离心处理，取上清液；所述上清液用第二萃取剂萃取，得到第二萃取液；将所述第二萃取液进行净化浓缩处理，得到待测样品溶液；测定所述待测样品溶液中丙烯酰胺的含量。通过丙烯酰胺溴化反应生成2,3-二溴丙酰胺，改变极性和溶解性，收集到有机相，便于净化处理，提高回收率；通过进一步净化浓缩，减少杂质峰，降低了检出限；最后用带电子捕获检测器的气相色谱仪测定，2,3-二溴丙酰胺在电子捕获检测器上有较高的响应值，具有更高的灵敏度。

Description

一种涂料制品中丙烯酰胺的测定方法 技术领域
本发明属于分析检测技术领域，特别涉及一种涂料制品中丙烯酰胺的测定方法。
背景技术
丙烯酰胺，具有神经毒性、生殖毒性、发育毒性、遗传毒性和致畸性等，国际癌症研究机构(IARC)将丙烯酰胺列为2类致癌物，即人类可能致癌物。世界各国都把丙烯酰胺列为危险化学品。丙烯酰胺应用广泛，可用于涂料、染料等合成工业。丙烯酰胺进入到环境中，可通过消化道、呼吸道、皮肤黏膜等多种途径进入人体，给环境和人类健康带来极大危害。
丙烯酰胺的测定方法有很多，如：高效液相色谱法、气相色谱法、气相色谱质谱法、液相色谱-串联质谱法。上述方法常用于食品、地下水、废水等样品中丙烯酰胺的测定，文献中未发现有测定涂料及其制品中丙烯酰胺的方法。
现有技术方案：
《GB5085.6-2007附录R固体废物丙烯酰胺的测定气相色谱法》针对污水样品，样品中的丙烯酰胺经溴水衍生化后，再用乙酸乙酯萃取浓缩，用电子捕获检测器的气相色谱法检测。
《GB5009.204-2014食品安全国家标准-食品中丙烯酰胺的测定》包括两种检测方法，第一种是以水为萃取剂，经固相萃取柱或基质分散固相萃取净化，以液相色谱-串联质谱法检测。第二种是用水萃取，萃取液用基质分散固相萃取净化，净化液经溴水衍生化后，再用乙酸乙酯萃取浓缩，气相色谱质谱法检测。
气相色谱-质谱法检测丙烯酰胺，检出限相对较高；液相色谱-串联质谱法仪器昂贵，成本高，难以普及；涂料及其制品样品基质通常比较复杂，杂质干扰多，目前还没有文献有关于涂料及其制品中丙烯酰胺测定方法的报道。因此，亟需开发一种检测涂料制品中丙烯酰胺的测定方法。
发明内容
针对上述问题，本发明公开了一种涂料制品中丙烯酰胺的测定方法，包括以下步骤：
将涂料制品粉碎；
粉碎后的所述涂料制品用第一萃取剂萃取，得到第一萃取液；
将所述第一萃取液依次进行溴化衍生处理、除溴处理和离心处理，取上清液；
所述上清液用第二萃取剂萃取，得到第二萃取液；
将所述第二萃取液进行净化浓缩处理，得到待测样品溶液；
测定所述待测样品溶液中丙烯酰胺的含量。
更进一步地，所述将涂料制品粉碎的具体步骤如下：
先用剪刀将涂料制品剪成小块，再用研磨器或粉碎机将块状涂料制品处理成细小颗粒。
更进一步地，所述第一萃取剂是质量分数为0.1％的乙酸溶液。
更进一步地，所述溴化衍生处理的具体步骤如下：
向所述第一萃取液中加入盐酸溶液，调节溶液的pH值至1～3；
向上述调节pH值后的第一萃取液中依次加入溴化钾和溴水，混合均匀，在0～2℃的黑暗条件下反应1h。
更进一步地，所述除溴处理使用的除溴剂为亚硫酸钠。
更进一步地，所述离心处理的条件为转速3000r/min，时间1～2min。
更进一步地，所述第二萃取剂是体积比为4：1的正己烷：乙酸乙酯混合溶液。
更进一步地，所述净化浓缩处理的具体步骤如下：
将所述第二萃取液进行浓缩处理，加入正己烷，进行二次浓缩处理，二次浓缩液转移至分液漏斗，边震荡边向分液漏斗中加入浓硫酸至第二萃取液无色澄清，静置分层后弃去下层浓硫酸；
向分液漏斗中加入饱和碳酸钾溶液，静置分层后保留有机相，浓缩至1～2mL，得到浓缩液；
向净化柱中加入正己烷，活化净化柱，再加入所述浓缩液，用洗脱剂洗脱，收集至浓缩杯中定容，得到待测样品溶液。
更进一步地，所述净化浓缩处理使用的洗脱剂是体积比为9：1的正己烷：乙酸乙酯的混合溶液。
更进一步地，所述净化柱的填料从上到下依次为无水硫酸钠、碱性硅胶、中性硅胶、酸性硅胶和中性硅胶。
与现有技术相比，本发明的有益效果是：通过丙烯酰胺溴化反应生成2,3-二溴丙酰胺，改变极性和溶解性，收集到有机相，便于净化处理，提高回收率；通过进一步净化浓缩，减少杂质峰，降低了检出限；最后用带电子捕获检测器的气相色谱仪测定，2,3-二溴丙酰胺在电子捕获检测器上有较高的响应值，具有更高的灵敏度。
本发明的其他特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。本发明的目的和其他优点可通过在说明书、权利要求书以及附图中所指出的结构来实现和获得。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1示出了根据本发明实施例的丙烯酰胺的标准曲线图；
图2示出了根据本发明实施例的待测样品溶液1的色谱图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地说明，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提出一种涂料制品中丙烯酰胺的测定方法，包括以下步骤：
S101、将涂料制品粉碎；
先用剪刀将涂料制品剪成小块，再用研磨器或粉碎机将块状涂料制品处理成细小颗粒，过60目筛。
本发明中，涂料制品主要包括油漆、建筑涂料、丙烯酸类乳液及其生产过程产生的固体废物等或者油漆、建筑涂料、丙烯酸类乳液等的废渣。本发明中描述的粉碎操作步骤只是其中一种，也可以采取其他常见的粉碎方法对涂料制品进行粉碎处理，得到相应的符合要求的样品。
S102、粉碎后的所述涂料制品用第一萃取剂萃取，得到第一萃取液；
第一萃取剂是质量分数为0.1％的乙酸溶液。目前现有的技术方案中通常采用纯水作为萃取剂，但目标物丙烯酰胺在水中的稳定性较差，因此本发明用0.1％的乙酸溶液代替纯水作为萃取剂，萃取涂料制品中的丙烯酰胺，进而提高目标物在萃取液中的稳定性，从而提高回收率。
S103、将所述第一萃取液依次进行溴化衍生处理、除溴处理和离心处理，取上清液；
向所述第一萃取液中加入盐酸溶液，调节溶液的pH值至1～3；
向上述调节pH值后的第一萃取液中依次加入溴化钾和溴水，混合均匀，在0～2℃的黑暗条件下反应1h，生成2,3-二溴丙酰胺；
边震荡边逐滴向上述溴化衍生处理后的第一萃取液中加入亚硫酸钠溶液，直至黄色完全消失为止，去除多余的溴水；
将上述除溴处理后的第一萃取液在3000r/min条件下离心1～2min，取离心后的上清液。
现有技术中，常用硫代硫酸钠去除未反应的溴，但会产生很多的杂质峰干扰，因此本发明采用亚硫酸钠作为除溴剂，亚硫酸钠是对有机物很惰性的试剂，不会对有机物产生影响，能够有效减少待测样品溶液的杂质峰。
S104、所述上清液用第二萃取剂萃取，得到第二萃取液；
将上清液转移至分液漏斗中，向分液漏斗中加入正己烷：乙酸乙酯作为第二萃取剂，混合、震荡放气后，静置分层，重复萃取两次，合并有机 相，得到第二萃取液。第二萃取剂采用体积比为4：1的正己烷：乙酸乙酯混合溶液，相比于现有仅使用乙酸乙酯作为萃取剂，能够减小乙酸乙酯在水中的溶解，提高萃取效果。
S105、将所述第二萃取液进行净化浓缩处理，得到待测样品溶液；
将所述第二萃取液进行浓缩处理至0.2～0.5mL，加入20mL正己烷，进行二次浓缩处理至10～15mL，二次浓缩液转移至分液漏斗，边震荡边向分液漏斗中加入浓硫酸至第二萃取液无色澄清，静置分层后弃去下层浓硫酸；
向分液漏斗中加入饱和碳酸钾溶液，静置分层后保留有机相，浓缩至1～2mL，得到浓缩液；其中，饱和碳酸钾溶液用于中和溶液中多余的酸；
向净化柱中加入30～50mL正己烷，活化净化柱，再加入所述浓缩液，用80～100mL体积比为9：1的正己烷：乙酸乙酯的混合溶液洗脱，收集至浓缩杯中定容至1mL，得到待测样品溶液。
其中，净化柱的填料从上到下依次为无水硫酸钠、碱性硅胶、中性硅胶、酸性硅胶和中性硅胶。
净化浓缩处理能够有效去除待测样品溶液中的杂质，减小样品基质的干扰，降低检出限。
S106、测定所述待测样品溶液中丙烯酰胺的含量。
本发明采用带电子捕获检测器的气相色谱仪测定待测样品溶液中的丙烯酰胺的含量。
本发明实施例中使用的试剂和设备如下。
试剂和材料：
乙酸乙酯：农残级；
正己烷：农残级；
丙烯酰胺标准溶液：浓度为100mg/L，溶剂为甲醇；
3mol/L盐酸溶液：量取250mL浓盐酸，缓慢加入盛有适量纯水的容量瓶中，加水稀释至IL；
溴化钾(KBr)；
碳酸钾(K 2CO 3)；
饱和溴水(溴的质量分数≥3％)；
4.0mol/L亚硫酸钠溶液：称取50.4g亚硫酸钠溶于少量水中，稀释至100mL；
无水硫酸钠：于400℃下灼烧4h，冷却后装入磨口玻璃瓶中，置于干燥器中保存；
除非另有说明，分析时均使用符合国家标准的分析纯试剂和蒸馏水，所使用试剂均可以通过商业途径购买。
仪器和设备：
气相色谱仪(带电子捕获检测器)；
浓缩装置：旋转蒸发仪，也可使用浓缩仪等性能相当的设备；
磁力搅拌器(带磁力搅拌子)；
万分之电子天平；
分液漏斗：250mL；
碘量瓶：250mL；
微量注射器：10μL、50μL、250μL。
气相色谱仪参考条件：
(1)色谱柱：DB-5石英毛细管柱(30m×0.25mm×0.25um)或等同柱；
(2)柱升温程序：180℃保持2.2min，以20℃/min速度升至280℃，并保持2min；
(3)柱流速：1～2mL/min，优选为1.5mL/min；
(4)进样口温度：220℃；
(5)检测器温度：300℃；
(6)进样量：1μL；
(7)分流比：1:1；
(8)载气：氮气，纯度≥99.999％。
实施例：
使用粉碎机将涂料制品粉碎，过60目筛，涂料制品为某涂料公司生产丙烯酸类乳液的废渣；
称取5.29g涂料制品样品置于碘量瓶中，加入50mL0.1％的乙酸溶液萃取样品，得到第一萃取液；
向第一萃取液中加入盐酸溶液，混匀，调节pH值至1，向第一萃取液中加入8g溴化钾并溶解，然后加入10mL溴水，混和均匀，在0℃黑暗条件下反应1h，生成2,3-二溴丙酰胺；边震荡边逐滴向上述溴化衍生处理后的第一萃取液中加入亚硫酸钠溶液，直至黄色完全消失为止，去除多余的溴水，将上述除溴处理后的第一萃取液在3000r/min条件下离心2min，取离心后的上清液；
上清液转移至分液漏斗，向分液漏斗中加入25mL正己烷：乙酸乙酯混合溶液(体积比为4：1)作为第二萃取剂，混合、振荡放气后，静置分层，重复萃取两次，合并有机相，得到第二萃取液；
将第二萃取液浓缩至约0.2mL，加入20mL正己烷，继续浓缩至约15mL，将溶剂置换为正己烷，转移到分液漏斗，边振荡边向分液漏斗中加入浓硫酸，至第二萃取液无色澄清，静置分层，弃去下层浓硫酸，加入10mL饱和碳酸钾溶液，静置分层，保留有机相，浓缩至2mL，得到浓缩后的待测样品溶液；
准备填料净化柱，填料从上到下依次为无水硫酸钠、碱性硅胶、中性硅胶、酸性硅胶和中性硅胶，质量分别为4g、2g、3g、8g和3g；先向净化柱中加入30mL正己烷，上柱进行活化，弃去该部分洗液，再加入浓缩后的待测样品溶液，用80mL正己烷：乙酸乙酯混合溶液(体积比为9：1)洗脱，收集至浓缩杯中，放入浓缩仪，用氮气定容至1mL，得到待测样品溶液1，放入气相色谱仪测定。
取上述同一涂料制品5.09g，根据上述方法得到待测样品溶液2，放入气相色谱仪测定。
绘制标准曲线：
取100μL丙烯酰胺标准溶液用甲醇定容至1mL，配制成10μg/mL的丙烯酰胺标准中间液；
取6只250mL碘量瓶，各加入50mL质量分数为0.1％的乙酸溶液，分 别加入0.5μL、5μL、10μL、20μL、50μL、100μL丙烯酰胺标准中间液，配制成丙烯酰胺含量分别为5ng、50ng、100ng、200ng、500ng、1000ng的丙烯酰胺标准系列待测溶液。按照涂料制品的制备步骤进行衍生、净化、浓缩，按推荐的色谱条件进行测定，以标准系列待测溶液中丙烯酰胺的含量(x,ng)为横坐标，对应的色谱峰响应值(峰面积y)为纵坐标，绘制标准曲线，如图1所示，具体数据见表1。标准曲线为y＝36.20161x，线性相关系数R 2为0.99984。
表1丙烯酰胺标准待测溶液具体参数
名称 丙烯酰胺含量(ng) 峰面积
丙烯酰胺标准待测溶液1 5 204.2388
丙烯酰胺标准待测溶液2 50 2019.3893
丙烯酰胺标准待测溶液3 100 3662.8398
丙烯酰胺标准待测溶液4 200 7358.4019
丙烯酰胺标准待测溶液5 500 18354.7032
丙烯酰胺标准待测溶液6 1000 36036.2015
待测样品溶液测定：
取1μL的待测样品溶液，注入气相色谱仪中，按推荐的色谱条件进行测定，如图2所示，丙烯酰胺色谱峰的保留时间为1.857min，峰面积为2418.9971。如表2所示，根据标准曲线得到待测样品溶液中的丙烯酰胺含量。
涂料制品中的丙烯酰胺浓度，按照下述公式进行计算：
Wi＝Ci/Mi；
其中：Ci为从标准曲线得到的丙烯酰胺含量(ng)，Mi为涂料制品的取样量(g)，Wi为涂料制品中丙烯酰胺的浓度(μg/kg)。
表2待测样品溶液具体参数
Figure PCTCN2021118390-appb-000001
空白实验：
用硅藻土(或石英砂)代替实际涂料制品，其他样品制备步骤均相同，在测试样品同时进行空白实验。经检测，空白实验中没有丙烯酰胺检出。
涂料制品加标回收率：
准确称取6份上述涂料制品样品，进行加标回收率测定，样品3、样品4、样品5的丙烯酰胺加标量均为10ng，样品6、样品7、样品8的丙烯酰胺加标量均为100ng，按照上述的制备步骤制备得到加标样品溶液3、加标样品溶液4、加标样品溶液5、加标样品溶液6、加标样品溶液7和加标样品溶液8，按照上述色谱条件进行测定。加标样品溶液3、加标样品溶液4和加标样品溶液5的平均加标回收率为75.1％，相对标准偏差为0.4％。加标样品溶液6、加标样品溶液7和加标样品溶液8的平均加标回收率78.4％，相对标准偏差2.0％，具体数据如表3所示。
表3涂料制品中丙烯酰胺的加标回收率
Figure PCTCN2021118390-appb-000002
方法检出限：
根据《环境监测分析方法标准制修订技术导则》(HJ168-2010)，称取5g空白样品，加入丙烯酰胺10ng，配置成浓度为2.00μg/kg的样品溶液，按照相同的样品制备步骤进行7次平行测定，计算得出7次的平均值为1.37μg/kg，相对偏差S为0.1028μg/kg，n＝7时，t值为3.143，因此确定本 发明的方法检出限(MDL＝t(n-1，0.99)×S)为0.32μg/kg。
虽然上文以丙烯酸类乳液的废渣为例进行了示例性说明，然而本发明并不限于此，其能够测定市面上的涂料制品以及涂料，比如油漆、建筑涂料、丙烯酸类乳液等或者油漆、建筑涂料、丙烯酸类乳液等的废渣。本领域技术人员可以根据本发明的测定原理以及实际应用情况综合考量，只要能实现本发明的原理即可。
本发明中提出的一种涂料制品中丙烯酰胺的测定方法，通过丙烯酰胺溴化反应生成2,3-二溴丙酰胺，改变极性和溶解性，收集到有机相，便于净化处理，提高回收率；通过进一步净化浓缩，减少杂质峰，降低了检出限；最后用带电子捕获检测器的气相色谱仪测定，2,3-二溴丙酰胺在电子捕获检测器上有较高的响应值，具有更高的灵敏度。
尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

  1. 一种涂料制品中丙烯酰胺的测定方法，其特征在于，包括以下步骤：
    将涂料制品粉碎；
    粉碎后的所述涂料制品用第一萃取剂萃取，得到第一萃取液；
    将所述第一萃取液依次进行溴化衍生处理、除溴处理和离心处理，取上清液；
    所述上清液用第二萃取剂萃取，得到第二萃取液；
    将所述第二萃取液进行净化浓缩处理，得到待测样品溶液；
    测定所述待测样品溶液中丙烯酰胺的含量。
  2. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述将涂料制品粉碎的具体步骤如下：
    先用剪刀将涂料制品剪成小块，再用研磨器或粉碎机将块状涂料制品处理成细小颗粒。
  3. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述第一萃取剂是质量分数为0.1％的乙酸溶液。
  4. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述溴化衍生处理的具体步骤如下：
    向所述第一萃取液中加入盐酸溶液，调节溶液的pH值至1～3；
    向上述调节pH值后的第一萃取液中依次加入溴化钾和溴水，混合均匀，在0～2℃的黑暗条件下反应1h。
  5. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述除溴处理使用的除溴剂为亚硫酸钠。
  6. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述离心处理的条件为转速3000r/min，时间1～2min。
  7. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述第二萃取剂是体积比为4：1的正己烷：乙酸乙酯混合溶液。
  8. 根据权利要求1所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述净化浓缩处理的具体步骤如下：
    将所述第二萃取液进行浓缩处理，加入正己烷，进行二次浓缩处理，二次浓缩液转移至分液漏斗，边震荡边向分液漏斗中加入浓硫酸至第二萃取液无色澄清，静置分层后弃去下层浓硫酸；
    向分液漏斗中加入饱和碳酸钾溶液，静置分层后保留有机相，浓缩至1～2mL，得到浓缩液；
    向净化柱中加入正己烷，活化净化柱，再加入所述浓缩液，用洗脱剂洗脱，收集至浓缩杯中定容，得到待测样品溶液。
  9. 根据权利要求8所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述净化浓缩处理使用的洗脱剂是体积比为9：1的正己烷：乙酸乙酯的混合溶液。
  10. 根据权利要求8所述的涂料制品中丙烯酰胺的测定方法，其特征在于，所述净化柱的填料从上到下依次为无水硫酸钠、碱性硅胶、中性硅胶、酸性硅胶和中性硅胶。
PCT/CN2021/118390 2021-09-07 2021-09-15 一种涂料制品中丙烯酰胺的测定方法 WO2023035293A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111044662.5 2021-09-07
CN202111044662.5A CN113777192B (zh) 2021-09-07 2021-09-07 一种涂料制品中丙烯酰胺的测定方法

Publications (1)

Publication Number Publication Date
WO2023035293A1 true WO2023035293A1 (zh) 2023-03-16

Family

ID=78841489

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/118390 WO2023035293A1 (zh) 2021-09-07 2021-09-15 一种涂料制品中丙烯酰胺的测定方法

Country Status (2)

Country Link
CN (1) CN113777192B (zh)
WO (1) WO2023035293A1 (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107356683A (zh) * 2017-05-22 2017-11-17 安徽宏远职业卫生技术服务有限公司 一种气相色谱法测定工作场所空气中丙烯酰胺的方法
CN111257455A (zh) * 2020-02-13 2020-06-09 山东省食品药品检验研究院 一种食用油中丙烯酰胺的测定方法
CN111289673A (zh) * 2020-03-06 2020-06-16 浙江省疾病预防控制中心 一种粮食制品中丙烯酰胺的检测方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309399C (zh) * 2000-10-25 2007-04-11 国家中药制药工程技术研究中心 复方双黄连制剂及制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107356683A (zh) * 2017-05-22 2017-11-17 安徽宏远职业卫生技术服务有限公司 一种气相色谱法测定工作场所空气中丙烯酰胺的方法
CN111257455A (zh) * 2020-02-13 2020-06-09 山东省食品药品检验研究院 一种食用油中丙烯酰胺的测定方法
CN111289673A (zh) * 2020-03-06 2020-06-16 浙江省疾病预防控制中心 一种粮食制品中丙烯酰胺的检测方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ALAIN, P. ET AL.: "Trace level determination of acrylamide in cereal-based foods by gas chromatography-mass spectrometry", JOURNAL OF CHROMATOGRAPHY A, vol. 1035, no. 1, 30 April 2004 (2004-04-30), XP004500718, ISSN: 0021-9673, DOI: 10.1016/j.chroma.2004.02.037 *
WANG JIYANG: "Study on Determination of Acrylamide in Water by Gas Chromatography", WATER TECHNOLOGY, vol. 14, no. 4, 31 August 2020 (2020-08-31), pages 55 - 57, XP093045201, ISSN: 1673-9353, DOI: 10.3969/j.issn.1673-9353.2020.04.013 *
YANG SICHAO, ZHANG HUI, WANG JUNHAN, CHEN FANG: "Quantification of acrylamide in foods by gas chromatography-mass spectrometry coupled with pro-column derivatization", SEPU - CHINESE JOURNAL OF CHROMATOGRAPHY, HUAXUE ZAZHI CHUBANSHE, DALIAN, CN, vol. 29, no. 5, 4 July 2011 (2011-07-04), CN , pages 404 - 408, XP093045203, ISSN: 1000-8713, DOI: 10.3724/SP.J.1123.2011.00404 *

Also Published As

Publication number Publication date
CN113777192B (zh) 2023-08-08
CN113777192A (zh) 2021-12-10

Similar Documents

Publication Publication Date Title
Babaee et al. Micellar extraction and high performance liquid chromatography-ultra violet determination of some explosives in water samples
CN106872617B (zh) 水产品中苯并咪唑及噻唑类残留药物的快速提取及lc-ms-ms检测方法
CN110780009B (zh) 一种超高效液相色谱-串联质谱法同时检测果蔬中7种酰胺类农药残留的方法
CN113391015A (zh) 一种土壤中14种酚类化合物的检测方法
CN109459506B (zh) 一种用于茶叶中多氯联苯检测的快速样品前处理方法
WO2023035293A1 (zh) 一种涂料制品中丙烯酰胺的测定方法
CN111721864B (zh) 高效液相色谱法快速测定小麦粉及其添加剂中非食用物质三聚硫氰酸三钠盐的方法
Korkisch et al. Determination of seven trace elements in natural waters after separation by solvent extraction and anion-exchange chromatography
CN113009038A (zh) 一种同时采集和检测大气环境中气相和颗粒相有机胺的分析方法
CN109847407B (zh) 一种戊柔比星的纯化方法
CN111289673A (zh) 一种粮食制品中丙烯酰胺的检测方法
CN111085006A (zh) 一种环境中有机污染物提取工艺
CN107543868A (zh) 一种测定含铁尘泥中氯离子含量的方法
Chang et al. ICP-OES determination of trace metal ions after preconcentration by 4-(8-hydroxy-5-quinolylazo) naphthalenesulfonic acid modified silica gel
CN113237978A (zh) 一种番茄中金刚烷胺和金刚乙胺的检测方法
KR100461702B1 (ko) 수질 시료 중에 잔류하는 글리포세이트, 엔도탈,클로람벤의 동시 검출법
CN110988214A (zh) 一种检测羟丙基类变性淀粉中氯丙醇的方法
CN112964822A (zh) 一种d-2-氨基丁醇中有关物质l-2-氨基丁酸的分析和分离方法
CN113307761B (zh) 一种分离蒽油中咔唑的方法
CN112816578B (zh) 一种含氨基小分子蘑菇毒素的检测方法以及一种试剂盒
CN114487189B (zh) 一种基于分散萃取技术测定食品中黄曲霉毒素b1的方法
CN114324660B (zh) 一种气相色谱质谱联用仪检测土壤和/或沉积物中灭多威肟的方法
KR100504303B1 (ko) 수질 시료 중에 잔류하는 에틸렌티오우레아, 말레산히드라지드, 이소프로필메틸포스포네이트의 동시 검출법
CN115508470B (zh) 一种乳粉中五氯苯酚含量的检测方法
CN114910594B (zh) 一种提取和衍生同步进行的草甘膦快速测定方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21956470

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE