本文關(guān)鍵詞： 烷基化反應(yīng) 氯化聚丙烯 稀釋比 動力學(xué) 紅外光譜 核磁共振 凝膠色譜 相容性　出處：《鄭州大學(xué)》2006年碩士論文　論文類型：學(xué)位論文

【摘要】：Friedel-Crafts烷基化反應(yīng)是有機(jī)合成和藥物合成中的一類重要反應(yīng)，有著十分廣泛的應(yīng)用。近年來，一些研究者將其應(yīng)用到了高分子領(lǐng)域，他們以聚合物作為烷化劑，通過烷基化反應(yīng)達(dá)到對聚合物進(jìn)行改性的目的，取得了較好的效果。在本文中，選取氯化聚丙烯(CPP)作為烷化劑，重點(diǎn)研究了它與甲苯的烷基化反應(yīng)的一些規(guī)律，建立了動力學(xué)模型，希望能通過烷基化反應(yīng)，用苯環(huán)取代CPP分子鏈上的部分氯原子，改變其分子結(jié)構(gòu)，降低其分子極性，使改性后的CPP與一些樹脂的相容性改善，擴(kuò)大其應(yīng)用范圍。 首先，從兩個(gè)方面改進(jìn)了測定氯含量的燃燒-中和法，提出了更為準(zhǔn)確更適合于該研究體系的氧瓶燃燒．電位滴定法。一是用電位滴定取代指示劑滴定來確定終點(diǎn)；二是數(shù)據(jù)處理采用Origin軟件擬合滴定曲線方程，由方程參數(shù)計(jì)算氯含量，求得的結(jié)果比微商法更準(zhǔn)確。為后文反應(yīng)動力學(xué)的研究奠定了基礎(chǔ)。 稀釋比是指良溶劑中允許加入非溶劑的最大量。對濃度、溫度和氯含量對稀釋比的影響規(guī)律分別進(jìn)行了研究，發(fā)現(xiàn)稀釋比隨濃度的增大而減小，隨溫度的升高而增大，隨氯含量的降低而變大。 然后，重點(diǎn)研究了三氯化鋁催化下CPP與甲苯的烷基化反應(yīng)。正交實(shí)驗(yàn)表明催化劑用量對反應(yīng)的影響最大，其次是反應(yīng)溫度和物料配比，反應(yīng)時(shí)間影響最小。進(jìn)而，測定了一組動力學(xué)數(shù)據(jù)，提出了動力學(xué)模型，求得了模型參數(shù)，并得到了動力學(xué)方程：dx／dt=2.37×10~5×[Cat]~3×exp(48794／RT)×(1-x)~(9.77)。對模型的可靠性也進(jìn)行了檢驗(yàn)。 接著，用三角相圖考察了離子液體、甲苯和氯化聚丙烯三元體系的分層區(qū)域，用于指導(dǎo)后續(xù)實(shí)驗(yàn)的設(shè)計(jì)。研究了離子液體對該反應(yīng)的催化性能，測定了一組動力學(xué)數(shù)據(jù)，建立了動力學(xué)模型，通過數(shù)據(jù)擬合得到了模型參數(shù)和動力學(xué)方程：dx／dt=1.62×[Cat]~(2.57)×exp(30159／RT)×(1-x)~(8.45)。該方程與三氯化鋁作催化劑時(shí)的動力學(xué)方程形式相同，都表現(xiàn)出較高的反應(yīng)級數(shù)。另外對離子液體的重復(fù)使用性能也進(jìn)行了討論。 采用IR和NMR技術(shù)證實(shí)了苯環(huán)基團(tuán)成功連接到CPP分子鏈上。用GPC測
[Abstract]:Friedel-Crafts alkylation is one of the most important reactions in organic synthesis and drug synthesis. In recent years, some researchers have applied it to the field of polymer. In this paper, chlorinated polypropylene (CPP) was selected as the alkylating agent, and some rules of alkylation of CPP with toluene were studied. A kinetic model was established to improve the compatibility of the modified CPP with some resins by using benzene ring to replace some chlorine atoms in the molecular chain of CPP, to change its molecular structure, to reduce its molecular polarity, and to improve the compatibility of the modified CPP with some resins through the alkylation reaction. The scope of its application is expanded. Firstly, the combustion-neutralization method for the determination of chlorine content is improved from two aspects, and a more accurate and more suitable oxygen flask combustion-potentiometric titration method is proposed. One is to use potentiometric titration instead of indicator titration to determine the end point. Secondly, the titration curve equation is fitted by Origin software, and the chlorine content is calculated by the parameters of the equation. The results obtained are more accurate than those obtained by the microquotient method, which lays a foundation for the later study of reaction kinetics. Dilution ratio is the maximum amount of non-solvent allowed in a good solvent. The effects of concentration, temperature and chlorine content on the dilution ratio are studied respectively. It is found that the dilution ratio decreases with the increase of concentration and increases with the increase of temperature. The content of chlorine increases with the decrease of chlorine content. Then, the alkylation of CPP with toluene catalyzed by aluminum trichloride was studied. The orthogonal experiment showed that the amount of catalyst had the most influence on the reaction, followed by the reaction temperature and material ratio, and the reaction time was the least. A set of kinetic data was measured, a kinetic model was put forward, parameters of the model were obtained, and the kinetic equation: DX / DT = 2.37 脳 10 ~ (5) 脳 [Cat] 3 脳 exp4794 / RT) 脳 1 ~ (-1) -x ~ (-) -7 ~ (-7) ~ 7 ~ (7). The reliability of the model was also tested. Then, the delamination region of ternary system of ionic liquid, toluene and chlorinated polypropylene was investigated by triangular phase diagram to guide the design of subsequent experiments. The catalytic performance of ionic liquid to the reaction was studied, and a set of kinetic data was determined. A kinetic model was established, and the model parameters and kinetic equation: 1. 62 脳 [Cat] 2. 57) 脳 exp1. 30159 / RT) 脳 1-x ~ (-) ~ (-) ~ (8. 45) are obtained by data fitting. The equation is the same as the kinetic equation when aluminum chloride is used as catalyst. The reusability of ionic liquids is also discussed. IR and NMR techniques were used to confirm that the benzene ring group was successfully connected to the CPP molecular chain. GPC was used to determine the molecular chain.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2006
【分類號】：O631

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