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自由基聚合是《高分子化学》学习的重要内容,其中动力学链长、平均聚合度、自由基寿命是三个重要的学术概念,理清三者之间的定量关系以于自由基聚合的理论学习颇有帮助。本文试图对这一内容进行讨论。 相似文献
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自动加速效应是自由基聚合宏观动力学的重要特征,对聚合过程和聚合产物有着重要的影响;有关自动加速效应的内容也是自由基聚合动力学教学的重难点之一。为帮助学生较好地理解和掌握自动加速效应相关内容,本文结合有关高分子化学教材,对自动加速效应的实验现象、与体型缩聚凝胶化过程的区别、产生原因、结果和影响因素等问题进行了总结和讨论。 相似文献
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自由基聚合是高分子化学课程中的重要一章,自由基聚合动力学(包括聚合速率、平均相对分子质量及分布)是教学中的重要内容。本文讨论了建立自由基聚合微观动力学模型的基础:三个基本假设和四个简化条件,阐释了传统单官能度引发剂引发的聚合体系速率方程推导中这些假设和条件的运用,并扩展到双官能度引发剂体系,得到基元反应速率和总速率。提出从三个层次讨论影响自由基聚合速率的因素,深化了对自由基聚合速率教和学。 相似文献
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自由基聚合是《高分子化学》课程的重要一章 ,其中 ,平均聚合度是自由基聚合微观动力学的重要研究内容。正确理解其概念 ,掌握各种数学表达式的涵义 ,对高分子化学的学习十分有益 ,本文对不同终止和链转移情况下平均聚合度的表述方法进行了讨论 相似文献
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二、聚合反应与共聚合聚合反应与共聚合反应一直是高分子合成与改性的重要内容与手段,近年仍有重要发展。下面就自由基聚合、共聚合、正负离子聚合等方面的研究概况进行简要地阐述。1.自由基聚合近年的研究主要在开发含功能基的烯类单体、新型自由基引发体系和引发机理、聚合动力学尤其高转化的聚合动力学等。李笃信等研究了 N-乙烯基咔唑在 znO 为分散 相似文献
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自由基聚合是高分子化学学习中的重难点。聚合速率、聚合度与聚合度分布都是重要的学习内容,偶合终止、歧化终止及链转移都会使聚合度的分布有差异,且相关文献和教材在链转移情况下对聚合度分布的影响分析的较少,本文从自由基聚合度推导方法出发,对自由基聚合涉及不同终止方式及链转移情况下的聚合度分布进行探讨。本文侧重于对存在链转移的情况下的两种计算方式进行详细地分析,并与实验结果进行对比,从而说明两种计算方式的特点和造成偏差的原因,得出了详细的理论结果,以有助于初学者更好地理解和研究该部分的相关内容。 相似文献
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自由基聚合近20年的发展 总被引:6,自引:1,他引:5
自由基聚合是在上世纪50年代发展起来的,已成为工业生产高分子产品的重要技术。自由基聚合由通用自由基聚合而发展为今天的活性/控制自由基聚合,是近20多年的事情。通用自由基合的研究主要是高活性引发剂、氧化还原体系及多功能引发体系,ESR和激光技术在动力学和自由基精细结构测定的应用等。而活性自由基聚合由最初的引发转移终止剂活性自由基聚合(iniferter),演变为氮氧自由基调控聚合(NMP)或稳定自由基聚合(SFRP),原子转移自由基聚合(ATRP),茂钛金属/环氧化物自由基开环引发聚合,可逆加成断裂链转移(RAFT)聚合,碘转移自由基聚合和有机碲、有机锑调控聚合等活性/控制自由基聚合。本文就以上各方面的研究进展进行简要的综述。 相似文献
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Satoshi Inoue Takeo Kumagai Hajime Tamezawa Hiroyuki Aota Akira Matsumoto Katsutoshi Yokoyama Yasuo Matoba Michirou Shibano 《Journal of polymer science. Part A, Polymer chemistry》2011,49(1):156-163
For a deeper understanding of allyl polymerization mechanism, the reinitiation efficiency of resonance‐stabilized monomeric allyl radical was pursued because in allyl polymerization it is commonly conceived that the monomeric allyl radical generated via the allylic hydrogen abstraction of growing polymer radical from monomer, i.e., “degradative monomer chain transfer,” has much less tendency to initiate a new polymer chain and, therefore, this monomer chain transfer is essentially a termination reaction. Based on the renewed allyl polymerization mechanism in our preceding article, the monomer chain transfer constant in the polymerization of allyl benzoate was estimated to be 2.7 × 10?2 at 80 °C under the polymerization condition, where the coupling termination reaction of growing polymer radical with allyl radical was negligible and, concurrently, the reinitiation reaction of allyl radical was enhanced significantly. The reinitiation efficiencies of monomeric allyl radical were pursued by the dead‐end polymerizations of allyl benzoate at 80, 105, and 130 °C using a small amount of initiators; they increased remarkably with raised temperature. Thus, the enhanced reinitiation reactivity of allyl radical at an elevated temperature could bias the well‐known degradative monomer chain transfer characteristic of allyl polymerization toward the chain transfer in common vinyl polymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
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自由基聚合动力学是高分子化学教学和学习中的重要内容。本文讨论了建立自由基聚合微观动力学模型的三个简化条件和三个基本假设,三个简化条件和三个基本假设是微观动力学研究聚合速率和聚合度的基础;同时也较为深入地探讨了动力学链长的物理意义、利用动力学链长概念建立起来的平均聚合度计算通用公式以及该公式的使用条件。 相似文献
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Living radical polymerization of diisopropyl fumarate to obtain block copolymers containing rigid poly(substituted methylene) and flexible polyacrylate segments
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Living radical polymerizations of diisopropyl fumarate (DiPF) are carried out to synthesize poly(diisopropyl fumarate) (PDiPF) as a rigid poly(substituted methylene) and its block copolymers combined with a flexible polyacrylate segment. Reversible addition‐fragmentation chain transfer (RAFT) polymerization is suitable to obtain a high‐molecular‐weight PDiPF with well‐controlled molecular weight, molecular weight distribution, and chain‐end structures, while organotellurium‐mediated living radical polymerization (TERP) and reversible chain transfer catalyzed polymerization (RTCP) give PDiPF with controlled chain structures under limited polymerization conditions. In contrast, controlled polymerization for the production of high‐molecular‐weight and well‐defined PDiPF is not achieved by atom transfer radical polymerization (ATRP) and nitroxide‐mediated radical polymerization (NMP). The block copolymers consisting of rigid poly(substituted methylene) and flexible polyacrylate segments are synthesized by the RAFT polymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2136–2147 相似文献
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Poli R 《Angewandte Chemie (International ed. in English)》2006,45(31):5058-5070
Controlled radical polymerization has come along in leaps and bounds following the development of efficient transition-metal catalysts for atom-transfer radical polymerization. Another type of controlled radical polymerization process, namely organometallic radical polymerization, uses the reversible formation of metal-carbon bonds. Metals are also implicated in catalytic chain transfer, a process that involves the abstraction of hydrogen atoms. This Minireview discusses the importance of one-electron transition-metal reactivity in metal-mediated controlled radical polymerization processes. 相似文献
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The free‐radical polymerization of vinyl monomers in the presence of dibenzyl trithiocarbonate (DBTTC) and under 60Co γ‐irradiation is of living character. Under 60Co irradiation, the bonds between benzyl group and sulfur were cleaved, benzyl radicals initiate the polymerization. The propagating radical together with trithiocarbonate radicals form a dormant polymer chain. The fast equilibrium between propagation radical and dormant polymer chain controls the polymerization. 相似文献
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活性自由基聚合经过十多年的发展,已成为一种有效的高分子设计手段.代表性的活性自由基聚合技术包括氮氧调控自由基聚合(NMP),原子转移自由基聚合(ATRP)和可逆加成-断裂链转移(RAFT)聚合或通过黄原酸酯交换法设计大分子(MADIX).这些技术已成功应用到多数共轭单体上,但对非共轭单体的聚合控制还不太成功.本文总结了几类适合非共轭单体的活性自由基(共)聚合方法,主要有RAFT/MADIX体系,某些ATRP体系,碘退化转移体系及近年新出现的有机碲调控自由基聚合(TERP)和有机锑调控自由基聚合(SBRP)体系,其中,TERP和SBRP的独特性值得关注. 相似文献
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