本文選題：RAFT聚合　切入點：環(huán)管反應(yīng)器　出處：《浙江大學(xué)》2017年碩士論文

【摘要】：聚合物的分子量分布是影響其力學(xué)和加工性能的重要參數(shù),如何通過反應(yīng)器操作方式調(diào)控實現(xiàn)聚合物分子量分布的精確定制極具挑戰(zhàn)。本文受工業(yè)環(huán)管反應(yīng)器的啟示,將其與可控“活性”自由基聚合技術(shù)相結(jié)合,進行多峰分子量分布聚合物的設(shè)計與定制。研究中以丙烯酸丁酯(BA)的甲苯溶液可逆加成-斷裂鏈轉(zhuǎn)移(RAFT)自由基聚合為模型體系,以3-苯甲基三硫代羧基丙酸(BCPA)為RAFT試劑,分別研究了 BA的間歇、連續(xù)管式及連續(xù)環(huán)管反應(yīng)器中RAFT溶液聚合的反應(yīng)動力學(xué)規(guī)律,揭示通過可調(diào)節(jié)管內(nèi)單程停留時間和循環(huán)分率實現(xiàn)對聚合物多峰分子量分布的精確調(diào)控技術(shù)。研究表明管式反應(yīng)器具有較好的傳熱傳質(zhì)能力,可有效地抑制間歇RAFT聚合中常見的誘導(dǎo)期,管內(nèi)反應(yīng)物能實現(xiàn)均勻混合從而減少擴散影響。連續(xù)環(huán)管反應(yīng)器中,通過調(diào)控管內(nèi)單程停留時間(τ)和循環(huán)分率,可定制具有預(yù)定多峰分子量分布的聚合物。不同循環(huán)分率的聚合體系經(jīng)3τ后達到穩(wěn)態(tài)且轉(zhuǎn)化率基本不變,聚合物低分子量部分保持不變,而高分子量部分不斷增大,該變化規(guī)律可通過理想高斯峰按幾何分布的質(zhì)量分率疊加模型得到定量解釋。本工作率先提出了循環(huán)管式反應(yīng)器與可控“活性”自由基聚合相結(jié)合的新技術(shù),用于多峰分子量分布聚合物的設(shè)計與定制,其分子量分布可通過理想高斯峰按幾何分布的質(zhì)量分率疊加模型進行預(yù)測,這為連續(xù)地調(diào)控聚合物分子量分布進而生產(chǎn)可控多峰分布聚合物新材料提供了新思路。
[Abstract]:The molecular weight distribution of polymer is an important parameter that affects its mechanical and processing performance. How to realize the precise customization of polymer molecular weight distribution through reactor operation is a challenge.Based on the inspiration of industrial loop reactor, the design and customization of multi-peak molecular weight distribution polymer were carried out by combining it with controllable "active" radical polymerization technology.In this study, the batch of BA was studied by the reversible addition-break chain transfer radical polymerization of butyl acrylate (BA) in toluene solution as model system, and the use of 3-phenylmethyl trithiocarboxypropionic acid (BCPA) as RAFT reagent.The kinetics of RAFT solution polymerization in a continuous tube reactor and a continuous loop reactor reveals the precise control technology of polymer multi-peak molecular weight distribution by adjusting the one-pass residence time and cyclic fraction in the tube.The results show that the tubular reactor has good heat and mass transfer ability and can effectively suppress the common induction period in batch RAFT polymerization. The reactants in the tube can be homogeneously mixed and the diffusion effect can be reduced.In a continuous loop reactor, the polymer with predetermined multi-peak molecular weight distribution can be customized by regulating the one-pass residence time (蟿) and the circulation fraction in the tube.The polymerization system with different cyclic fraction reached steady state after 3 蟿 and the conversion was basically unchanged, the low molecular weight part of the polymer remained unchanged, while the high molecular weight part of the polymer increased continuously.The law of variation can be quantitatively explained by the mass fraction superposition model of the geometric distribution of the ideal Gao Si peak.In this work, a new technique of combining the cyclic tubular reactor with controllable "active" radical polymerization is proposed, which can be used in the design and customization of multi-peak molecular weight distribution polymers.The molecular weight distribution can be predicted by the superposition model of mass fraction of ideal Gao Si peak according to geometric distribution, which provides a new idea for the continuous regulation of polymer molecular weight distribution and the production of new polymer materials with controllable multi-peak distribution.
【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】：O631.5

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