苯并口恶嗪-环氧化合物-胺类催化剂体系开环聚合反应的研究

采用TLC，GPC，1H－NMR及IR等分析方法，对苯并恶嗪－环氧化合物－胺类催化剂体系的聚合反应进行了研究，表征了产物结构，并探讨了聚合反应机理，结果表明，苯并恶唪－环氧化合物体系在胺类催化剂如苄胺，咪唑的作用下，能发生开环聚合反应，生成低分子量的聚合物。     

纳米聚N-异丙基丙烯酰胺微凝胶的光引发聚合

选择具有温敏性的高分子单体N－异丙基丙烯酰胺（N－isopropylacrylamide，NIPAM）为主单体，N，N′－亚甲基双丙烯酰胺（methylenebisacrylamide，MBA）为交联剂，运用光引发无皂乳液聚合的方法合成出粒径小于100nm的高分子微凝胶，并研究了在改变体系组成和条件时微凝胶粒径的变化。结果显示，在乳化剂临界胶束浓度以下，随着乳化剂浓度的提高，微凝胶粒子的粒径不断关小且趋向稳定；相比于热引发，产生的微凝胶具有较高的单分散性而且粒径较小。     

Probing the early stages of polymerization of ethylene on a model chromium/silica catalyst by Fourier transform infrared spectroscopy

The nature of the interaction of monomer, and the early stages of growth of oligomers of ethylene on a rather more uniform surface of Cr/SiO₂ catalyst than hitherto studied has been investigated by differenceFTIR spectroscopy using C₂D₄ and C₂H₄ as reactants both with and without subsequent treatment of the catalyst with CO andTHF. The active catalyst was prepared by reaction of vapour phase CrO₂Cl₂ with the vicinal hydroxyls of the silica surface. Three distinct kinds of methylene groups were detected. Arguments are given for assigning the peaks at 2935 and 2860 cm^–1 to CH₂ groups directly bound to the active site and those at 2920 and 2850 to CH₂s in the growing chain well removed from the Cr. The peaks at 2160 and 2165 cm^–1 are attributed to CD₂ groups hydrogen bonded to surface hydroxyls.     

工业聚合反应装置 Ⅴ.流化床气相聚合反应器

简介了流化床气相聚合反应器的原理和6种典型的聚合装置。     

阳离子化多元醇防塌剂的研制

室内研究和现场应用表明,聚乙烯醇类防塌剂表现出较明显的增粘负效应,可引起钻井液粘度的急剧增加,严重影响其推广应用.通过金属盐催化降解和阳离子化反应,研制出了抑制性好且增粘负效应低的阳离子化改性多元醇防塌剂.考察了阳离子化试剂、反应温度、反应时间对取代度、反应效率和产品主要性能的影响,得出了阳离子化多元醇防塌剂最佳制备条件,即：PVA与阳离子化试剂物质的量比为1：1,反应温度为50℃,反应时间为4 h,阳离子度可达0.435.     

助催化剂对TiCl_4/MgCl_2催化丙烯高温聚合的影响

研究了助催化剂种类(三甲基铝、三异丁基铝、三正己基铝、三乙基铝和甲基铝氧烷)及其含量对无内、外给电子体的TiCl4/MgCl2催化剂催化丙烯高温(100℃)聚合性能的影响,并用结晶分级分析、示差扫描量热和凝胶渗透色谱等方法分析了所得聚丙烯的结晶熔融行为和微观结构。实验结果表明,聚合温度从70℃升至100℃时,TiCl4/MgCl2催化剂的定向能力基本不变;100℃聚合时,以烷基化能力较弱的三异丁基铝为助催化剂时TiCl4/MgCl2催化剂的活性最高,而采用烷基化能力最强的三甲基铝为助催化剂时TiCl4/MgCl2催化剂的活性最低;100℃聚合时,助催化剂的种类对TiCl4/MgCl2催化剂的定向能力影响很小。     

负载化非茂单活性中心催化剂乙烯聚合的研究

在硅胶上负载了双(N-环己基-3-叔丁基水杨醛亚胺基)二氯化锆配合物,得到负载化非茂单活性中心催化剂。该催化剂用于乙烯聚合,考察了配合物用量、共聚单体1-己烯用量、聚合温度、聚合压力、聚合时间、三乙基铝用量对乙烯聚合性能的影响及对聚合物的相对分子质量、相对分子质量分布、熔体流动指数和密度的影响。实验结果表明,负载化非茂单活性中心催化剂保持了原均相催化剂的乙烯聚合性能;该催化剂在淤浆聚合工艺中聚合平稳,所得聚合物的颗粒形态良好。     

Effect of surfactants on phenol removal by the method of polymerization and precipitation catalysed by Coprinus cinereus peroxidase

The removal of phenol by peroxidase‐catalysed polymerization was examined using Coprinus cinereus peroxidase in the presence of surfactants. The non‐ionic surfactants with poly(oxyethene) residues, Triton X‐100, Triton X‐405 and Tween 20, enhanced the phenol removal efficiency at a level similar to high relative molecular mass poly(ethylene glycol) (relative molecular mass 3000). Although the improvement in the removal efficiency was less than that of Triton X‐100, Span 20, sodium lauryl sulfate (SDS) and lauryl trimethylammonium bromide (DTAB) also enhanced the removal efficiency. The requirement of the enzyme for almost 100% removal of 100 mg dm^?3 phenol decreased to one‐fourth by the addition of 30 mg dm^?3 Triton X‐100. Triton X‐100, Triton X‐405, Tween 20 and DTAB could reactivate the enzyme precipitated with the phenol polymer, leading to the restarting of the phenol removal reaction. Copyright © 2003 Society of Chemical Industry     

甲基丙烯酸三氟乙酰氧乙酯的聚合

对甲基丙烯酸三氟乙酰氧乙酯(TFAOEMA)的阴离子聚合及原予转移自由基聚合进行了研究。常用的阴离于引发剂如丁基锂、1，1-二苯基已基锂等很难引发TFAOEMA的阴离子聚合，而碱性较弱的引发剂如三乙基铝却容易引发，且产率较高。以氯化亚铜、五甲基二乙基三胺、溴代丙酸乙酯为引发体系的TFAOEMA的本体原子转移自由基聚合符合活性聚合特征。但在四氢呋喃为溶剂的原子转移自由基聚合中却存在活性中心失活现象。以末端含卤素的聚甲基丙烯酸甲酯为大分子引发剂，引发TFAOEMA的原子转移自由基聚合，得到了含氟双嵌段聚合物。     

Copolymerization of bromophenylmaleimide with ethyl or butyl methacrylate

N‐p‐Bromophenylmaleimide (BrPMI) does not polymerize in solution by conventional free radical mechanism. However, it readily polymerized in bulk when mixed with a free radical initiator and heated in a microwave oven for 7–8 min. Copolymerization of ethyl methacrylate or butyl methacrylate with BrPMI was conducted in dioxane. The copolymers were characterized by IR and ¹H NMR spectroscopy and gel permeation chromatography. The monomer reactivity ratios were calculated by a non‐linear least‐square analysis. Thermal analysis indicated a great improvement in thermal stability of the copolymers compared with the methacrylate homopolymers. BrPMI was also polymerized in bulk in the DSC pan, which allowed the calculation of the activation energy of its polymerization. Copyright © 2003 Society of Chemical Industry