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摘要: 端羟基聚丁二烯广泛应用于生产胶黏剂和密封剂。如今，由于它独特的物理化学特性像：热解性、弹性、韧性、耐久性，在复合固体推进剂中它更是作为燃料粘合剂来使用。为了获得这些特性需要在端羟基聚丁二烯的非极性聚合物链上引入一个或多个环氧官能团。这些聚合物，包含非共轭的碳碳双键，可以增加它们的极性并改善功能。
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官能团的相互转化是合成新颖的功能化聚合物，引入反应性官能团和对非共轭的二烯烃类聚合物进行化学修饰的普遍、通用的方法。通过环氧化反应在聚合物的分子骨架上引入一个新的活性官能团是既有效又方便的，这个方法有很好的性能和广泛的应用性。
在不同的反应条件包括反应时间、反应温度和其他条件下端羟基聚丁二烯的环氧化能力被详细地研究了而且产物也用核磁光谱进行了表征。此外，在较高的反应温度和较长的反应时间下，发生副反应的可能性也随之增加。
直接用氧气使烯烃发生环氧化是较为困难的，因此选择适合的催化剂成为环氧化反应的关键。金属离子-酞菁配体具有独特的催化活性，在温和的条件下就能催化氧化各类有机反应，本文选用金属酞菁作催化剂，并将其用于端羟基聚丁二烯的分子氧催化环氧化反应。
本论文探索端羟基聚丁二烯的环氧化反应，考察催化剂的性能，对该反应的影响因素进行了讨论，得出最佳的反应条件为：反应温度40℃，反应时间8h，通氧量 40 mL/min，CoPc/Al2O3 催化剂用量2%，醛烯比为2.5:1，环氧化物产率为67.05%。6219
关键词： 端羟基聚丁二烯；环氧化聚合物；金属钛菁
Study on the Epoxidation of Hydroxyl-terminated Polybutadiene
Abstract: Hydroxyl-terminated polybutadiene is widely used in making adhesives and sealants. Nowadays, it is especially used as a fuel binder in composite solid propellants thanks to such unique physicochemical properties as pyrolysis, elasticity, toughness, and durability. These properties are achievable by introducing one or more epoxy functional groups in non-polar polymer chains. These polymers, which contain non-conjugated carbon–carbon double bonds, tend to increase in polarity and improve in functionality.
Functional group inter-conversion (FGI) is a common and versatile method for synthesizing novel functionalized polymers, introducing reactive functional groups and chemical modification of non-conjugated polydiene polymers. Introducing a new reactive functional group into the polymer backbone can be conveniently and effectively achieved through epoxidation, which leads to superior properties and a wide variety of applications.
The oxidation ability of hydroxyl-terminated polybutadiene was studied in detail at different reaction circumstances including various reaction times 、temperatures and other circumstances and the products were identified using 1H-NMR. In addition, it has been found that at high reaction temperatures and longer times, the possibility of side-products increases.
It is difficult to form olefin epoxidation directly using oxygen. Therefore, it is a key to select suitable catalysts in the epoxidation reaction. Metal ion phthalocyanine ligand has a unique catalytic activity and can catalyze the oxidation of all kinds of organic reactions under mild conditions. In this paper the metal phthalocyanine was selected as the catalyst. It was used for the catalytic epoxidation of hydroxyl-terminated polybutadiene with molecular oxygen.
In order to explore the epoxidation reaction of hydroxyl-terminated polybutadiene, to investigate the catalysts properties, and to discuss the reaction factor. The optimum condition was obtained with 40℃, time 8h, molecular oxygen 40mL/min, amount of CoPc/Al2O3 catalyst 2%, ratio of aldehyde and cyclohexene 2.5:1, with 67.05% epoxide product.
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