功能分子印迹聚合物催化剂的设计、合成及自控制催化作用研究

发布时间：2018-07-23 12:36

【摘要】：催化是现代化学工业的基石,分子印迹及其高选择性催化作用是当前催化技术取得的最重要进展之一。然而,催化的实际应用通常涉及多步骤反应及选择性可调的催化作用过程,现有印迹聚合物及催化剂无法迎合这一时代发展的需求。本文从分子设计着手,迎合这一挑战,发展出可分别进行连续催化的分子印迹催化剂及选择性可调的分子印迹催化剂。为实现连续催化反应,本文将金属纳米粒子与功能分子印迹聚合物结合起来,制备出了可连续催化水解和还原的分子印迹催化剂。研究以2-丙烯酰胺-2-甲基丙磺酸(磺酸根为酸性活性中心)为功能单体,以对硝基苯酚及双(对硝基苯酚)碳酸酯为双模板,以Au纳米粒子为金属活性中心,制得了可连续催化的分子印迹催化剂。其酸中心则允许双(对硝基苯酚)碳酸酯进行水解,其金属中心则允许后续还原得以进行,由此实现了连续的催化作用。同时,由于载体为分子印迹聚合物,故合成的催化剂不仅具有连续催化的功能,而且具有高选择性的特性。在此基础上,本文还为了克服当前分子印迹研究中选择性可调的困境,以9-癸烯酸为功能单体,以对羟基苯甲醛为模板分子,以Ag纳米粒子为金属活性中心制备出了选择性可调的分子印迹催化剂。其中,9-癸烯酸中的链结构为合成的分子印迹催化剂构筑了可流动分子链,从而对底物通道构成调制作用。低温条件下,合成聚合物中的分子链被冻结,故合成的印迹聚合物对特异性底物对羟基苯甲醛具有分子识别的能力,允许其抵近Ag纳米粒子,从而使催化成为可能;反之,高温条件下,印迹聚合物内分子链热运动的加强,造成了印迹聚合物中的识别位点被破坏,合成的印迹聚合物对特异性底物分子识别能力无法体现,选择性下降,故其对特异性底物的还原与对底物类似物的还原作用基本相似,无选择性差别。从而,以这种独特的方式,合成的印迹聚合物催化剂呈现出选择性/非选择性-可调节的催化特性。通过以上二部分较系统的工作,本文发展出了可分别进行连续催化的分子印迹催化剂及选择性可调的分子印迹催化剂,阐明了分子印迹催化剂催化作用的规律,为更有效地使用分子印迹聚合物催化剂提供了必要的理论及实验依据。
[Abstract]:Catalysis is the cornerstone of modern chemical industry. Molecular imprinting and its high selective catalysis are one of the most important advances in current catalytic technology. However, the practical application of catalysis usually involves multistep reactions and selective and adjustable catalytic processes. The existing imprinted polymers and catalysts are unable to meet the needs of the development of this era. In order to achieve continuous catalytic reaction, this paper combines metal nanoparticles with functional molecularly imprinted polymers to prepare molecules that can catalyze hydrolysis and reduction continuously in order to achieve continuous catalytic reaction. 2- acrylamide -2- methyl propane sulfonic acid (acidic active center of sulfonic acid) was used as a functional monomer, with p-nitrophenol and bis (p-nitrophenol) carbonate as a double template and Au nanoparticles as the metal active center, a continuous catalytic molecular imprinting catalyst was prepared. Its acid center allowed double (p-nitrophenol). At the same time, as the carrier is a molecularly imprinted polymer, the catalyst not only has a continuous catalytic function, but also has a high selectivity. On this basis, this paper also overcame the molecular imprinting research. In the study, a selective and adjustable molecular imprinting catalyst was prepared by using 9- decenoic acid as a functional monomer, with P hydroxybenzaldehyde as a template molecule and Ag nanoparticles as the metal active center. The chain structure of 9- decenoic acid was used as a molecularly imprinted catalyst to construct a mobile molecular chain, thus the substrate was made to the substrate. The molecular chain in the synthetic polymer is frozen at low temperature, so the synthetic imprinted polymer has the ability to identify the specific substrate to hydroxybenzaldehyde, allowing it to close to the Ag nanoparticles, thus making it possible; conversely, the thermal movement of the molecular chain within the imprinted polymer is strengthened under high temperature conditions. The recognition site in the imprinted polymer is destroyed, and the synthetic imprinted polymer is unable to reflect the specific substrate molecular recognition ability and the selectivity decreases. Therefore, the reduction of the specific substrate is basically similar to the reduction of the substrate analogues, and there is no selective difference. From this, the imprinted polymer is synthesized in this unique way. The catalyst exhibits selective / non selective catalytic properties. Through the systematic work of the above two parts, the molecular imprinting catalyst and the selective and adjustable molecular imprinting catalyst, which can be catalyzed by continuous catalysis, are developed. The law of the catalytic action of the molecular imprinting catalyst is clarified, so as to use the molecules more effectively. The imprinted polymer catalyst provides the necessary theoretical and experimental basis.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;O631.3

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