發(fā)布時間：2018-03-19 09:37

  本文選題：全氟辛基磺酰氟　切入點：衍生化反應(yīng)　出處：《浙江大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：全氟辛基磺酰氟(Perfluorooctane sulfonyl fluoride, PFOSF),是全氟辛基磺酸類化合物的主要前體。PFOSF因具有特殊的化學(xué)性質(zhì),表面活性、熱穩(wěn)定性、耐酸性以及疏水疏油性,而廣泛應(yīng)用于生產(chǎn)與生活中如紡織品涂層、染色劑、泡沫滅火器、皮革等行業(yè)。PFOSF具有鍵能最強(qiáng)的C-F鍵,其極大的穩(wěn)定性導(dǎo)致該類化合物難以在環(huán)境介質(zhì)中化學(xué)降解及生物降解；并且可在生物體內(nèi)放大、富集。截至目前有高達(dá)45250噸的PFOSF直接或間接排放到土壤、水體、大氣中,對環(huán)境造成較大威脅。此類化合物具有遠(yuǎn)距離遷移能力和一定的生物毒性,因此在2009年,全氟辛烷磺酰氟、全氟辛烷磺酸及其鹽類、全氟辛酸及其鹽類作為新型持久性有機(jī)污染物(POPs)被添加到《斯德哥爾摩公約》的附件B中。PFOSF由于其結(jié)構(gòu)的特殊性,分子中缺乏可離子化基團(tuán)及發(fā)色團(tuán),難以通過液相色譜質(zhì)譜聯(lián)用技術(shù)(LC/MS)對其進(jìn)行分析檢測。有關(guān)此類化合物在環(huán)境樣品中的含量研究尚屬空白。論文著重探討PFOSF的LC/MS檢測方法及其在環(huán)境樣品分析中的應(yīng)用。本論文主要分為以下三個部分：1.首先對全氟化合物進(jìn)行綜述,主要概述了全氟化合物的生產(chǎn)方式、結(jié)構(gòu)、種類、性質(zhì)、用途、毒性、人類健康風(fēng)險評估、全球傳輸理論,并且對全氟化合物的樣品前處理方法、儀器分析研究進(jìn)展、不同環(huán)境介質(zhì)中的分布情況進(jìn)行了概述。同時,對PFOSF的生產(chǎn)、性質(zhì)、用途,以及國內(nèi)外研究進(jìn)展進(jìn)行概述。2.以PFOSF作為主要研究對象,建立其氧化還原衍生化方法,進(jìn)而通過LC-MS/MS技術(shù)對此類化合物進(jìn)行定量分析檢測。實驗對不同衍生化試劑以及催化劑進(jìn)行比較,最終優(yōu)選出對甲苯硫酚作為衍生化試劑、三乙胺作為催化劑。此外,本文考察了對甲苯硫酚、三乙胺的用量以及衍生化時間對產(chǎn)率的影響,并優(yōu)化了LC-MS/MS方法的檢測條件,進(jìn)而實現(xiàn)該化合物的定量分析檢測。考察了方法的適用性獲得了較好的實驗結(jié)果,PFOSF的線性檢測范圍為0.5-200 ng/mL,線性相關(guān)系數(shù)r2為0.9991,檢出限為0.1 pg。3.環(huán)境水體中PFOSF的富集及檢測：采用液-液萃取方式,對甲苯硫酚作為衍生化試劑,通過標(biāo)準(zhǔn)加入法對色譜質(zhì)譜級純水、自來水、運(yùn)河水進(jìn)行檢測。結(jié)果顯示不同時間所采集的自來水中PFOSF的平均含量為：1330-1700 ng/L;運(yùn)河水中PFOSF的平均含量為850 ng/L;色譜質(zhì)譜級純水中平均含量為500 ng/L。結(jié)果表明環(huán)境水體中普遍含有PFOSF,且明顯高于色譜質(zhì)譜級純水。同時對方法進(jìn)行驗證,檢出限為0.5 Pg,在低、中、高三個不同濃度水平的重復(fù)性RSD分別為10.88%,10.45%,8.45%。
[Abstract]:Perfluorooctane sulfonyl fluorofluorooctane (PFOSF) is the main precursor of perfluorooctane sulfonic acid compounds. PFOSF has special chemical properties, surface activity, thermal stability, acid resistance and hydrophobicity. PFOSF is widely used in textile coating, dyeing agent, foam fire extinguisher, leather and other industries. PFOSF has the strongest bond energy C-F bond, and its great stability makes it difficult to degrade this kind of compounds in environmental media. Up to now, up to 45250 tons of PFOSF has been directly or indirectly discharged into soil, water and atmosphere, which pose a great threat to the environment. Thus, in 2009, perfluorooctanesulfonyl fluoride, perfluorooctane sulfonic acid and its salts, perfluorooctanoic acid and their salts as new persistent organic pollutants, were added to Annex B of the Stockholm Convention. PFOSF was added to Annex B of the Stockholm Convention because of its structural specificity, The lack of ionization groups and chromophore in the molecules, It is difficult to analyze and detect PFOSF by liquid chromatography-mass spectrometry (LC / MS). The study on the content of these compounds in environmental samples is still blank. This paper focuses on the LC/MS detection method of PFOSF and its application in the analysis of environmental samples. This paper is divided into the following three parts: 1.First, a review of perfluorocarbons, The methods of production, structure, species, properties, uses, toxicity, human health risk assessment, global transport theory, sample pretreatment methods and instrumental analysis of perfluorinated compounds are reviewed. At the same time, the production, properties, uses and research progress of PFOSF are summarized. 2. Taking PFOSF as the main research object, the method of redox derivation is established. Then the quantitative analysis of these compounds was carried out by LC-MS/MS. Finally, p-methylthiophenol and triethylamine were selected as derivatization reagent and triethylamine as catalyst by comparing different derivatization reagents and catalysts. In this paper, the effects of the dosage of p-methylthiophenol, triethylamine and derivatization time on the yield were investigated, and the detection conditions of LC-MS/MS method were optimized. The linear detection range of PFOSF is 0.5-200 ng / mL, the linear correlation coefficient R2 is 0.9991, the detection limit is 0.1pg.3. the enrichment of PFOSF in environmental water is obtained. And detection: liquid-liquid extraction, As a derivatization reagent, p-methylthiophenol was used for the determination of pure water and tap water in chromatography-mass spectrometry by standard addition method. The results show that the average content of PFOSF in tap water collected at different times is 1: 1330-1700 ng / L; the average content of PFOSF in canal water is 850 ng / L; the average content in pure water of chromatography-mass spectrometry is 500ng / L. the results show that the average content of PFOSF in environmental water is 500ng / L. It contains PFOSFs and is obviously higher than pure water in chromatography-mass spectrometry. The detection limit was 0. 5 PG, and the reproducibility RSD of three different concentrations in low, middle and high levels were 10. 88 and 10. 45 and 8. 45, respectively.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.63;X830

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