本文選題：Cl原子 + 不飽和酯��； 參考：《山東大學(xué)》2017年碩士論文

【摘要】：不飽和酯及酮類化合物都屬于含氧揮發(fā)性有機(jī)化合物。環(huán)境中的不飽和酯及酮類化合物絕大部分來自人為排放。它們種類豐富,用途廣泛,常作為單體或者共聚物用于聚合物的生產(chǎn),如在涂料、樹脂、粘合劑、薄膜、合成纖維等生產(chǎn)過程中被廣泛應(yīng)用。其結(jié)構(gòu)中含有的碳碳雙鍵與羰基直接相連,使其化學(xué)性質(zhì)非�；顫�,在排放進(jìn)入環(huán)境后會(huì)由大氣中存在的Cl原子、OH自由基、NO_3自由基和O_3分子等所引發(fā)一系列氧化降解反應(yīng),生成二次有機(jī)污染物,從而對(duì)大氣的能見度和氧化能力產(chǎn)生影響,繼而導(dǎo)致二次氣溶膠的生成,對(duì)人類健康造成威脅。C1原子作為一種氧化劑,它所引發(fā)的不飽和揮發(fā)性有機(jī)化合物的氧化反應(yīng)已備受關(guān)注。因此,由Cl原子引發(fā)的不飽和酯及酮類化合物的大氣氧化過程的理論研究對(duì)于區(qū)域及全球大氣化學(xué)、氣候變化和環(huán)境效應(yīng)等方面的研究是有重要意義的。本文采用量子化學(xué)方法對(duì)兩種典型的不飽和酯類化合物--丙烯酸甲酯、丙烯酸乙酯,三種不飽和酮類化合物--3-戊烯-2-酮、4-己烯-3-酮、5-己烯-2-酮與C1原子的大氣氧化反應(yīng)分別進(jìn)行了研究,進(jìn)而對(duì)其大氣氧化機(jī)理和動(dòng)力學(xué)性質(zhì)做了全面的了解。研究結(jié)果總結(jié)如下:1.丙烯酸甲酯與Cl原子的反應(yīng)機(jī)理及動(dòng)力學(xué)研究采用密度泛函理論(Density Functional Theory,DFT)在 M06-2X/6-311+G(3df,2p)//M06-2X/6-31G(d,p)水平上對(duì)由Cl原子引發(fā)的丙烯酸甲酯的氧化反應(yīng)機(jī)理進(jìn)行分析。由此得到了詳細(xì)的反應(yīng)機(jī)理:Cl加成反應(yīng)、H抽提反應(yīng)和CH3抽提反應(yīng)三種路徑。Cl加成反應(yīng)在整個(gè)初級(jí)反應(yīng)中占據(jù)著主要地位。因而本文對(duì)其后續(xù)反應(yīng)進(jìn)行研究并得到了這些反應(yīng)的產(chǎn)物。CH3抽提反應(yīng)因其反應(yīng)的勢(shì)壘很高而難以發(fā)生,因此該反應(yīng)可以不被考慮。應(yīng)用MESMER程序計(jì)算了在198-648 K的溫度區(qū)間內(nèi)各初級(jí)反應(yīng)的速率常數(shù)。結(jié)果顯示:Cl原子加成到端基碳上的反應(yīng)路徑更容易發(fā)生,而抽提-CH3中的H的反應(yīng)也不容忽視。在298 K和760 Torr的條件下,計(jì)算所得的總包反應(yīng)速率為1.66×10-10 cm3 molecule-1 s-1。在所研究的溫度區(qū)間內(nèi),總包反應(yīng)速率常數(shù)隨溫度升高反而降低,也就是說與溫度呈現(xiàn)出負(fù)相關(guān)性。2.丙烯酸乙酯與與Cl原子的反應(yīng)機(jī)理及動(dòng)力學(xué)研究由C1原子所引發(fā)的丙烯酸乙酯的全面的、合理的氧化反應(yīng)機(jī)理在M06-2X/6-31 1+G(3df,2p)//M06-2X/6-31G(d,p)水平上被計(jì)算得到。該反應(yīng)主要包括八個(gè)反應(yīng)通道:兩個(gè)C1加成C=C雙鍵的反應(yīng)和六個(gè)H抽提的反應(yīng)。通過比較計(jì)算結(jié)果,我們得知Cl加成到C=C雙鍵的反應(yīng)較易發(fā)生。然而,對(duì)于甲基和亞甲基上的H抽提反應(yīng)也存在一定的競(jìng)爭(zhēng)性�；赗ice-Ramsperger-Kassel-Marcus(RRKM)理論,本論文應(yīng)用MESMER程序計(jì)算并得到了初級(jí)反應(yīng)的速率常數(shù)。在298 K和760 Torr的條件下,計(jì)算得到的總包反應(yīng)速率為1.80×10-10 cm3 molecule-1s-1。且得知在198-648 K的范圍內(nèi),總的反應(yīng)速率常數(shù)會(huì)與溫度呈現(xiàn)出負(fù)相關(guān)性。此外,通過比較了 Cl原子與丙烯酸甲酯(MA)、丙烯酸乙酯、甲基丙烯酸甲酯(MMA)和烯丙基酯(AAC)的反應(yīng)速率,得知它們的大小關(guān)系為kMMA(cl)kEA(cl)kMA(cl)kAAC(cl)。通過計(jì)算,得出由Cl原子引發(fā)的EA的大氣壽命為154.3 h,與由其他氧化劑(如OH自由基,O_3分子和NO_3自由基)決定的EA的大其壽命相比,Cl原子引發(fā)的EA的大氣氧化反應(yīng)相當(dāng)重要。3.不飽和酮類化合物與Cl原子的反應(yīng)機(jī)理及動(dòng)力學(xué)研究由C1原子引發(fā)的三種不飽和酮類化合物:3-戊烯-2-酮、4-己烯-3-酮和5-己烯-2-酮的大氣氧化降解機(jī)理的研究在M06-2X/6-311+G(3df,2p)//M06-2X/6-31 G(d,p)水會(huì)平上進(jìn)行的。通過計(jì)算,給出了三種不飽和酮與Cl原子完整的反應(yīng)機(jī)理。反應(yīng)除了 Cl-加成反應(yīng)和H-抽提的反應(yīng)外,本文還考慮了抽提-CH3的反應(yīng)。對(duì)于前兩種反應(yīng)類型,Cl原子加成到碳碳雙鍵上的反應(yīng)占主導(dǎo)地位。其中Cl原子加成到末端碳原子上更為容易。而對(duì)于-CH3抽提反應(yīng),由于反應(yīng)能壘較高且需吸收大量熱量,可以被忽略。在O_2和NO存在下,論文對(duì)加成產(chǎn)物的后續(xù)反應(yīng)進(jìn)行了研究,得到了它們的主反應(yīng)路徑以及主產(chǎn)物,并進(jìn)行了相應(yīng)的比較。在一定的溫度(198-648 K)與壓力(76-2000 Torr)區(qū)間內(nèi),研究了各基元反應(yīng)的速率常數(shù)與溫度和壓力的關(guān)系。在所研究的溫度與壓力范圍內(nèi),速率常數(shù)呈現(xiàn)溫度負(fù)相關(guān)性,然而隨壓力變化的趨勢(shì)卻不明顯。通過計(jì)算得到了三種不飽和酮的大氣壽命。
[Abstract]:Unsaturated esters and ketones belong to volatile organic compounds. Most of the unsaturated esters and ketones in the environment are derived from human emissions. They are rich in variety and widely used, often used as monomers or copolymers for the production of polymers, such as in the production process of coatings, trees, adhesives, films, synthetic fibers, etc. It is widely used. The carbon carbon double bond in its structure is directly connected with the carbonyl group to make its chemical properties very active. After the discharge into the environment, a series of oxidative degradation reactions caused by the presence of Cl atoms, OH radicals, NO_3 radicals and O_3 molecules in the atmosphere will be produced to produce two organic pollutants and thus the visibility and oxygen of the atmosphere. The influence of chemical ability, which leads to the formation of two aerosols, threatens the human health to threaten the.C1 atom as an oxidant. The oxidation of the unsaturated volatile organic compounds caused by it has been paid much attention. Therefore, the theoretical study on the atmospheric oxidation process of unsaturated esters and ketones induced by Cl atoms The study of regional and global atmospheric chemistry, climate change and environmental effects is of great significance. In this paper, the atmospheric oxygen of two typical unsaturated esters, methyl acrylate, ethyl acrylate, three unsaturated ketones, --3- amyl -2- ketone, 4- hexene -3- ketone, 5- hexene -2- ketone and C1 atom, is used in this paper. The results are summarized as follows: 1. the reaction mechanism and kinetics of methyl acrylate and Cl atom are studied by density functional theory (Density Functional Theory, DFT) at the //M06-2X/6-31G (D, P) level of M06-2X/6-311+G (3DF, 2P). The oxidation reaction mechanism of Methyl Acrylate Initiated by Cl atom is analyzed. Thus the detailed reaction mechanism is obtained: the Cl addition reaction, the H extraction reaction and the CH3 extraction reaction are the main position of the three path.Cl addition reaction in the whole primary reaction. The.CH3 extraction reaction is difficult to occur because of the high potential barrier of the reaction. Therefore, the reaction can not be considered. The rate constant of the primary reactions in the temperature range of 198-648 K is calculated by using the MESMER program. The result shows that the reaction path of the Cl atom added to the end group is easier to occur, and the reaction of the H in the extraction -CH3 is not to be ignored. Under the conditions of 298 K and 760 Torr, the calculated total package reaction rate is 1.66 * 10-10 cm3 molecule-1 s-1. in the temperature range studied. The total reaction rate constant decreases with the temperature rise. That is to say, the reaction mechanism and kinetics of the negative correlation with the temperature and the reaction mechanism and kinetics of the C1 and the Cl atom are studied by C1. The overall and reasonable oxidation reaction mechanism of Ethyl Acrylate Initiated by the atom is calculated at M06-2X/6-31 1+G (3DF, 2P) //M06-2X/6-31G (D, P) level. The reaction mainly includes eight reaction channels: two C1 addition C=C double bonds and six H extracts. However, the H extraction reaction on methyl and methylene is also competitive. Based on the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, the MESMER program is used to calculate and obtain the rate constant of the primary reaction. The total reaction rate of the total package is 1.80 * 10-1 under the 298 K and 760 Torr strips. 0 cm3 molecule-1s-1. and in the range of 198-648 K, the total reaction rate constant will have a negative correlation with the temperature. In addition, by comparing the reaction rates of Cl atoms with methyl acrylate (MA), ethyl acrylate, methyl methacrylate (MMA) and allyl ester (AAC), they know that their size relation is kMMA (CL) kEA (CL) kMA. C (CL). By calculation, the atmospheric lifetime of EA caused by Cl atoms is 154.3 h, compared with the lifetime of EA determined by other oxidants such as OH free radicals, O_3 molecules and NO_3 free radicals. The EA atmospheric oxidation reaction initiated by Cl atoms is very important for the reaction mechanism and kinetics of the.3. unsaturated ketones with the atoms. Three kinds of unsaturated ketones induced by atoms: the atmospheric oxidation degradation mechanism of 3- amyl -2- ketone, 4- hexene -3- ketone and 5- hexene -2- ketone is carried out on the M06-2X/6-311+G (3DF, 2P) //M06-2X/6-31 G (D,). The reaction mechanism of the three unsaturated ketones with the atom is given. In addition to the reaction of H- extraction, this paper also considers the reaction of extracting -CH3. For the first two types of reaction, the reaction of Cl atoms added to carbon carbon double bonds is dominant. The addition of Cl atoms to the end carbon atoms is easier. For the -CH3 extraction reaction, the reaction energy barrier is high and the absorption of a large amount of heat can be ignored. In O_2 and N In the presence of O, the subsequent reactions of the added products were studied, and their main reaction paths and main products were obtained, and the corresponding comparisons were made. The relationship between the constant number of reaction rates of the basic elements and the temperature and pressure was studied at a certain temperature (198-648 K) and pressure (76-2000 Torr). The temperature and pressure studied were studied. In the range, the rate constant presents a negative correlation with temperature, but the trend of pressure variation is not obvious. The atmospheric lifetime of three unsaturated ketones is calculated.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.12

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本文編號(hào)：1902583