不同聚合机理的“聚合度”公式的讨论

从聚合反应的机理的角度,聚合反应分为逐步聚合和连锁聚合两类.连锁聚合按照引发"活性种"的差异又分为自由基聚合和离子聚合.离子聚合分为阳离子聚合、阴离子聚合和配位聚合.这些是所有<高分子化学>教材编排的重要线索.本文以自由基聚合、离子聚合、逐步聚合和配位聚合的机理为线索,进一步说明对<高分子化学>教材中关于聚合度公式的综合理解和融会,旨在提高学生对<高分子化学>重点内容和意义的认识和把握.     

高分子化学试题库系统的开发

利用当前通行的关系数据库技术、采用VB编程语言和ACCESS数据库 ,设计了高分子化学教学试题库系统应用软件———“试卷魔术师”。它由四个模块组成 ,即试题库模块、试卷分析模块、资料库模块和辅助模块。具有试题的录入、删除、修改和访查、手工或自动生成试卷、试卷分析以及资料查阅等诸多功能。满足授权的用户可以利用它随机抽卷、查阅相关资料及历史成绩等。它不仅可以作为高分子化学课程教师生成试卷、分析试卷的有力工具 ,又可作为本专业学生进行高分子化学试题训练、自学并阅读课外参考资料的有效手段。它使用方便 ,操作简单 ,针对性强 ,是一种较为实用的计算机辅助教学软件工具     

药学专业高分子化学的虚拟仿真教学探索——基于Python的自由基聚合反应模拟

通过Python语言开发了一款教学用自由基聚合反应数值模拟器FRPython。该程序通过对自由基聚合反应体系的常微分方程组进行数值模拟,得到引发剂自由基浓度、链自由基浓度、动力学链长,以及聚合度分布等信息。以聚甲基丙烯酸甲酯聚合体系的数值模拟为例,FRPython可直观有效地演示自由基聚合反应过程,同时避免了稳态假设、方程推演等较为深奥的内容,为药学专业高分子化学相关知识的教学提供有益参考。     

《高分子化学》课程在土建类本科院校的教学改革初探

《高分子化学》是高分子材料与工程专业四大专业基础课之一,作为该专业学生接触的第一门专业基础课,内容涵盖了高分子的基本概念、聚合方法、聚合反应类型和机理,是进一步学习其他专业课程的基础.本文根据高分子化学课程在土建类工科院校的现状,结合近年来高分子化学课程的教学实践与探索,从增加教学中建筑材料切入点、探索适应工科学生的互...     

原子转移自由基聚合与高分子构筑

活性聚合反应是目前高分子合成研究最为活跃的领域之一，原子转移自由基聚合反应（ATRP）是实现活性聚合的一种有效途径，可实现多种单体的活性聚合和可控自由基聚合。本文介绍了原子转移自由基聚合反应机理，重点综述了原子转移自由基聚合在高分子合成中的应用。     

《高分子化学》课程中开环聚合教学口诀及解析

开环聚合反应是高分子化学中的一类重要反应,但因开环聚合过程既涉及到了逐步聚合和连锁聚合的特点,又涉及到了阴离子聚合和阳离子聚合的基本方式,因此开环聚合反应一直都是《高分子化学》课堂教学的难点.笔者从课堂实际角度出发,结合开环聚合的基本概念和特征总结出一套口诀用于《高分子化学》中开环聚合反应章节教学,并详细解释了口诀中所...     

基于PLA制备的高分子化学理论与实践的有机结合

高分子化学课程以基本概念、聚合原理和基本聚合方法为主,按照聚合机理分为逐步聚合、自由基聚合、自由基共聚合、离子聚合和配位聚合.为避免课程理论教学过于空洞和抽象,作者以科研中乳酸为原料制备聚乳酸的合成过程为例,结合课程教学中聚合反应的基本原理,探讨了线性缩聚反应、阳离子开环聚合反应、阴离子开环聚合反应、配位聚合反应等反应机理,将理论教学与科研工作、生产实际相结合,使教与学达到双赢.     

我国高分子化学的研究现状和基金的管理导向

高分子化学是高分子科学的三大分支领域(高分子化学、高分子物理、高分子工程)之一,它的学科领域覆盖了聚合反应研究、高分子合成及高分子改性.由于高分子化学肩负着为高分子学科提供新高分子化合物的首要任务,因此是高分子科学的基础.我国从事高分子化学研究的科研人员,约占全部从事高分子研究人员的65%,因引高分子化学研究也是我国高分子科学研究队伍的主流(见表1).我国的高分子化学研究涉及新聚合反应及新聚合方法研究、聚合反应动力学研究、功能高分子的分子设计和     

能量最低原理在高分子化学教学中的应用探索

能量最低原理是自然界最普遍的规律之一,高分子化学中的许多现象都可以用它来加以解释。本文从聚合反应方向、自由基稳定性、聚合中的重排反应等几个方面阐述了能量最低原理在高分子化学中的具体体现,对用能量最低原理来解释高分子化学反应的规律和现象进行了初步探索。实践证明,在高分子化学教学中应用能量最低原理来讲解一些问题,会起到事半...     

自由基聚合反应的新介质——离子液体的新应用

离子液体具有独特的理化性能,作为一种环境友好、"可设计性"的溶剂,近年来成为化学领域的热点和前沿。离子液体作为自由基聚合反应的溶剂,对聚合速率、聚合产物结构及性能都有一定的影响。离子液体已经被较为广泛地应用于不同介质、不同物相中的自由基聚合反应,但是并不完全。近两年来已有研究工作者将离子液体应用于微乳液和气相中的自由基聚合反应,并和其他有机溶剂及水溶液共同调控自由基聚合反应。离子液体也首次应用于有机碲调控的自由基聚合反应和氮氧稳定的自由基聚合反应。同时离子液体也可以调控自由基聚合反应后聚合物的结构和形貌,是一种很好的进行聚合物自组装的溶剂。本文主要综述了近年来离子液体对自由基聚合反应的影响,特别是对聚合产物结构及性能的影响,最后展望了离子液体在聚合反应中的应用前景。     

可逆加成-断裂链转移自由基聚合研究进展

综述了活性/可控自由基聚合中的可逆加成-断裂链转移(RAFT)自由基聚合研究进展;总结了RAFT试剂、RAFT聚合反应条件、RAFT聚合物及其结构形貌的最新研究进展;指出RAFT自由基聚合反应已被作为重要方法之一用于合成具有特定分子结构的聚合物.     

Polymerization of Vinyl Monomers with Binary Initiator System of N-Chlorosuccinimide and Lewis Acids

The polymerization of vinyl monomers with a binary system composed of N-chlorosuccinimide (NCS) and some Lewis acids was investigated by means of kinetic and spectral determinations. It was found that the NCS-ZnCl₂ system was the most effective as an initiator of radical polymerization of methyl methacrylate, and this polymerization was initiated by a radical produced via the reaction of NCS and ZnCl₂, and terminated bimolecularly. By applying a spin trapping technique to the reaction of NCS with ZnCl₂, it was shown that the initiating radical was N-succinimidyl radical which was obtained through a homolysis at the N-Cl bond.     

Free-radical polymerization of methyl methacrylate in the presence of dithiobenzoates as reversible addition-fragmentation chain transfer agents

The pseudoliving radical polymerization of methyl methacrylate in bulk mediated by dithiobenzoates with various leaving groups as reversible addition-fragmentation chain-transfer agents has been studied. It has been shown that polymerization proceeds under conditions of the low steady-state concentration of radical intermediates; as a result, the steady-state of the process is rapidly achieved even at low conversions. Retardation of polymerization observed at high concentrations of reversible addition-fragmentation chain-transfer agents is apparently associated with the occurrence of chain termination reactions involving intermediates, as evidenced by the model reaction. The autoacceleration of polymerization is suppressed with an increase in the concentration of reversible addition-fragmentation chain-transfer agents. An efficient approach to the synthesis of a narrow-dispersed PMMA with the controlled molecular mass has been suggested.     

SIMULTANEOUS MEASUREMENT OF FREE RADICAL DECAY IN POLYMERIZATION OF MMA INITIATED BY AIBN USING ESR AND ITS KINETIC MODEL*

 The kinetics of free radical decay in the polymerization of MMA initiated by AIBN was studied by means of ESR spectroscopy. It was found that the curves of radical decay are strongly associated with the reaction temperature, the initiator concentration and the solvent. In the case of the radical polymerization carried out at high temperature or in solution, the radical concentration first reached a maximum, then declined monotonously with reaction time. It was also found that the greater the amount of initiator or the higher the temperature, the more rapidly the radicals decay. When the bulk polymerization was implemented at a relatively low temperature, the curves of radical decay became more complicated, i.e.,the radical concentration rapidly rose to a maximum, then dropped to a minimum, finally increased again with reaction time.Taking into account the diffusion effect, a semi-empirical equation is suggested to describe the kinetics of propagating radical decay.     

通过自由基抑制剂研究聚多巴胺的形成机理

利用自由基抑制剂二甲基亚砜(DMSO)与依达拉奉(Edaravone)研究了多巴胺(DA)聚合中可能存在的自由基聚合路径,并考察了p H值对聚合过程的影响.利用紫外-可见光谱跟踪了反应过程.研究结果表明,DMSO和Edaravone均可抑制DA的聚合,而且Edaravone的抑制作用更加显著.研究结果表明,自由基聚合路径存在于DA的聚合过程中.实验还发现,DA的聚合速率随着p H值的升高而增大,但不同p H值时溶液的最终外观基本一致.     

可逆加成-断裂链转移自由基共聚合研究进展

与其它可控/活性自由基聚合相比,可逆加成-断裂链转移(RAFT)自由基聚合具有适用单体范围广、反应条件温和、不受聚合实施方法的限制等优点,因此成为目前高分子合成研究最为活跃的领域之一.通过它不但实现了广泛单体的可控/活性聚合,还合成了嵌段、接枝、梳型、星型、无规及梯度等结构的聚合物.本文综述了RAFT自由基共聚合领域的研究进展,内容主要包括已报道的RAFT自由基共聚合反应体系和RAFT过程对共聚产物组成的影响.     

六甲氧基甲基三聚氰胺-多元醇-丙烯酸酯混杂聚合体系的研究

六甲氧基甲基三聚氰胺 (HMMM) 多元醇 丙烯酸酯 酸催化剂混杂聚合体系在高温下同时进行缩聚和自由基聚合并表现出协同效应 .体系中的活泼亚甲基在HMMM的催化下被空气氧化成过氧化氢物 ;过氧化氢物在酸催化下分解成自由基进而引发自由基聚合反应 .研究结果表明 ,体系中存在固化加速的协同效应 ;同时体系中还存在热互补效应 ,丙烯酸酯的自由基聚合反应放出的热可以传递给缩聚反应 ,满足缩聚反应吸热的要求 .混杂聚合得到的高分子合金膜具有优良的机械性能和耐溶剂性能 ,这是由于在混杂聚合过程中形成了互穿聚合物网络 (IPN)结构 .使用潜酸催化剂作为酸的来源 ,可以提高体系的储存稳定性 ;交联 引发剂的使用可以拓宽它的使用范围 ;对超枝化聚合物在混杂体系中的应用也进行了初步研究     

Ab initio Emulsion Polymerization by RAFT (Reversible Addition–Fragmentation Chain Transfer) through the Addition of Cyclodextrins

A novel process to produce homo‐ and copolymers by RAFT polymerization in emulsion is presented. It is known that RAFT‐controlled radical polymerization can be conducted in emulsion polymerization without disturbing the radical segregation characteristic of this process, thus leading to polymerization rates identical to those encountered in the corresponding nonliving systems. However, RAFT agents are often characterized by very low water solubility and, therefore, they diffuse very slowly from the monomer droplets, where they are initially solubilized, to the reaction loci, i.e., the polymer particles. Accordingly, when used in emulsion polymerization, they are practically excluded from the reaction. In this work, we show that cyclodextrins, well‐known for their ability to form water‐soluble complexes with hydrophobic molecules, facilitate the transport across the H₂O phase of the RAFT agent to the polymer particles. Accordingly, chains grow through the entire process in a controlled way. This leads to the production of low‐polydispersity polymers with well‐defined structure and end functionalities as well as to the possibility of synthesizing block copolymers by a radical mechanism.     

Macromonomers as well-defined building blocks in macromolecular engineering

The present work compares the efficiency of different polymerization methods to design well-defined comb-shaped structures based on macro monomers. Anionic polymerization remains the method of choice and allows the control of polymerization degree of the main chain and the length of the grafts. The presence of an active chain end on the backbone enabled the synthesis of a new type of hyperbranched polymers by reaction with appropriate low molar multifunctional compounds. Free radical polymerization is less efficient for the controlled homopolymerization of macromonomers but less sensitive to the presence of impurities. It requires in most cases long fractionation procedures to access well defined comb-shaped fractions characterized by high molar masses. The controlled free radical polymerization constitutes an interesting alternative. The homopolymerization of macromonomers with late transition metal catalysts was also examined and comb-shaped polymers characterized by a syndiotactic backbone and atactic grafts could be obtained.     

Emulsion polymerization of vinyl acetate. II

The emulsion polymerization of vinyl acetate was investigated at low ionic strengths and has quite unusual kinetics. The rate of polymerization is dependent on the initiator concentration to the first power and independent of soap concentration. In seeded polymerizations, the rate of polymerization depends on initiator to the 0.8 power, particle concentration to the 0.2 power, and monomer volume to 0.35 power. In all cases the rate of polymerization is almost independent of monomer concentration in the particles until 85–90% conversion. These results were rationalized by the following mechanism: (a) polymerization initiates in the aqueous phase because of the solubility of the monomer and is stabilized there by adsorption of ionic soap on the growing polymer molecule; (b) the growing polymer is swept up by a particle at a degree of polymerization (under our conditions) of about 50–200. Growth continues in the particle. This sweep-up is activation-controlled as both particle and polymer are charged. (c) Chain transfer to the acetyl group of monomer gives a new small radical which cyclizes to the water-soluble butyrolactonyl radical, and reinitiates polymerization in the aqueous phase; (d) the main termination step is reaction of an uncharged butyrolactonyl radical with a growing aqueous polymer radical. A secondary reaction at low ionic strength is sweep-up of an aqueous radical by a particle containing a radical. At high ionic strength, this is the major termination step. The unusual kinetic steps are justified by data from the literature. They are combined with the usual mechanisms operating for vinyl acetate polymerization and kinetic equations are derived and integrated. The integral equations were compared with the experimental data and shown to match it almost completely over the whole range of experimental variables.