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。     

Diffusion-controlled size-selective chloride ion sensing in the presence of bromide ion using a thin, nanoporous, plasma-polymerized coating on an Ag/AgCl electrode

We have developed a diffusion-controlled size-selective method for sensing chloride ion in the presence of bromide ion, based on a thin, nanoporous, plasma-polymerized coating of hexamethyldisiloxane on an Ag/AgCl electrode. Sub-nanometer-sized pores responsible for a highly cross-linked polymer network in the plasma-polymerized coating allowed diffusion-controlled permeation of chloride ion while blocking the larger bromide ion. An electrode coating of thickness greater than 70 nm enabled chloride detection in the concentration range 1-10 mM in the presence of 0.63 mM bromide ion. Advantages of this approach are: (1) simple design compared with ionophore-based strategies and (2) compatibility with microfabrication and mass production processes.     

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。     

低熔融指数聚丙烯的开发生产

总结了开发生产低熔融指数聚丙烯的试验过程与结果，通过优选催化剂、优化操作过程、控制加氢量，生产出质量稳定可靠的熔融指数在0．2～0．5g/l0min之间的低熔融指数聚丙烯．     

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     

核壳乳液聚合中甲基丙烯酸用量对印花制品的影响

采用核壳乳液聚合法合成涂料印花粘合剂，考察了甲基丙烯酸(MAC)用量的改变对印花产品的牢度和色光的影响：在核中，当MAC的用量分别为0．0g，0．2g，0．4g，0．6g时，干摩牢度分别为25，2．5 ，3,0，3．5，色光由暗变亮；在壳中当MAC的用量分别为0．0g，0.2g，0．4g，0．6g时，干摩牢度分别为2.5，2．5 ，3．0，3．5，色光变亮，对得色量和鲜艳度影响不大。     

Crystallization of Polymer-Derived Silicon Carbonitride at 1873 K under Nitrogen Overpressure

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 0.57SiC·0.43Si₃N₄·0.49C is studied as a function of nitrogen overpressure at 1873 K. The ceramic suffers a weight loss at p _N2 < 3.5 bar (1 bar = 100 kPa), does not show a weight change from 3.5 to 11 bar, and gains weight above 11 bar. The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar. The weight-loss transition, at 3.5 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si₃N₄ are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition. The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism. A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism. The supersaturation required to nucleate α-Si₃N₄ crystals is calculated to be 30 kJ/mol.     

乙炔黑吸附聚合制导电聚苯胺

用乙炔黑吸附化学聚合新工艺制备导电聚苯胺，可保持电导率不变，但转化率和堆密度提高，并明显改善了聚苯胺的颗粒形态和制膜加工性，使由其制备的聚苯胺复合正极膜和固体聚苯胺锂蓄电池的电化学性能得以改进。     

双环戊二烯聚合反应热力学和动力学研究

研究了ＤＣＰＤ－ＷＯＣｌ４－ＡｌＥｔ３体系前阶段的反应动力学，采用ＧＣ法分析了不同反应条件下的动力学数据，发现ｌｇ（［ＤＣＰＤ］０／［ＤＣＰＤ］）￣ｔ存在线性关系，说明该体系在前段的聚合反应为一链式反应符合二级反应模型。同时还对该体系聚合反应热力学也进行了研究；对聚合反应的ΔＨｐ、ΔＳｐ、ΔＧｐ进行了讨论。