无皂型乳液聚合的研究进展

综述了无皂型乳液聚合反应机理及影响乳液稳定性的因素。对无皂型乳液聚合制备方法进行了论述，并介绍了无皂型乳液聚合的研究动态、应用和发展前景。     

双膦胺镍-甲基铝氧烷体系催化苯乙烯聚合

研究了具有新型结构的双膦胺镍配合物N,N-双(二苯膦基)-对甲氧基苯胺二氯化镍-甲基铝氧烷(PNP-N i-MAO)催化体系对苯乙烯聚合的催化性能,考察了聚合温度、n(A l)∶n(PNP-N i)、PNP-N i的浓度和苯乙烯的浓度对催化活性、苯乙烯转化率、聚苯乙烯相对分子质量及其分布的影响,并用核磁共振和凝胶色谱对聚苯乙烯的结构进行了表征。实验结果表明,在聚合温度25℃、聚合时间1h、n(A l)∶n(PNP-N i)=300、c(苯乙烯)=2.3m ol/L、c(PNP-N i)=0.4mm ol/L、甲苯为溶剂的适宜条件下,苯乙烯的转化率可达95%以上,催化活性达到5×105g/(m ol.h)左右。核磁共振和凝胶色谱表征结果显示,所得聚苯乙烯为无规结构,重均相对分子质量约为1×104,相对分子质量分布Mw/Mn约为2。     

Ring‐opening polymerization of lactones initiated by diphenylzinc–coinitiator systems

Diphenylzinc, alone or in combination with water and butanone as coinitiators, was used as a polymerization initiator system for a variety of lactones at varying temperatures. The resulting data indicate that the course of the polymerization is greatly influenced by the lactone structure, as well as by the molar ratio of coinitiator to diphenylzinc. When used alone, diphenylzinc exhibited high activity as an initiator in δ‐valerolactone polymerizations, although it was less efficient when used in the β‐butyrolactone and the β‐propiolactone polymerizations. Activity in the polymerization of β‐lactones was increased by adding small amounts of butanone or water. It was also observed that the diphenylzinc–butanone combination was more effective than the diphenylzinc–water mixture in the polymerizations of β‐butyrolactone and β‐propiolactone. Copyright © 2003 Society of Chemical Industry     

FCC汽油叠合生产柴油的研究——(Ⅰ)叠合催化剂的研制

采用中孔γ-Al2O3为载体，以非贵金属Ni为活性金属组分，以金属Sn为助剂组分，制备了FCC汽油叠合生产柴油的催化剂。在实验室小型连续流动式固定床装置上，以FCC汽油为原料，考察了主活性金属负载量、助催化剂、催化剂制备条件对催化剂性能的影响。研究结果表明，在活性金属Ni质量分数为8％，助催化剂Sn质量分数为1％，浸渍时间6h，焙烧温度500℃，焙烧时间4h的条件下，制备的叠合催化剂的催化性能最好。并对催化剂进行了1500h的稳定性试验和再生性能考察，结果表明该叠合催化剂具有良好的稳定性和再生性能。     

Monte Carlo simulation of gas phase polymerization of 1,3‐butadiene. Part II: Kinetics optimization and confirmation

Studies on the deactivations and initiations of gas phase polymerizations of 1,3‐butadiene have been achieved by Monte Carlo simulation. Initiation and deactivation control the reaction before and after the peak of the polymerization rate, respectively. The influence of polymerization temperature has been studied. Monte Carlo modeling of polymerization kinetics and mechanism was confirmed by the agreement of experimental data and simulation results of polymerizations run with a temporary evacuation of monomer. The balance of catalysts and active chains is established by both initiation and chain transfer reactions with cocatalyst, which causes a ‘pseudo‐stability’ stage. © 2003 Society of Chemical Industry     

Inhibition of radical polymerization in solvent‐based systems (security of solvent‐based radical polymerization of PSA‐acrylic in a plant reactor)

This article shows the influence of some chain‐transfer agents as inhibitors for acrylic solvent‐based polymerization. These chain‐transfer agents can offer significant advantages, as outlined below. The following chain‐transfer agents were studied to stop or slow down the polymerization process in the case of a runaway: n‐dodecyl mercaptan, trimethylolpropane‐trimercaptoacetate, phenothiazine, diphenylphenylen diamine, cuprum oxide, isopropanol, toluene, and carbon tetrachloride. Synthesized pressure‐sensitive adhesive based on acrylic polymers and containing 2‐ethylhexyl acrylate, methyl acrylate, and acrylic acid were used for the production of self‐adhesives with high cohesion. The polymerization was accomplished in ethyl acetate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1354–1357, 2003     

无机阻燃剂高聚合度聚磷酸铵的研制

以五氧化二磷、磷酸铵盐、尿素为原料、氨气为保护气,制备了高聚合度聚磷酸铵无机阻燃剂。考察了五氧化二磷、磷酸铵盐、尿素的用量和反应温度对聚磷酸铵平均聚合度的影响。采用端基滴定法测定了聚磷酸铵的聚合度,并用X射线衍射(XRD)法表征了聚磷酸铵的晶体结构,同时测定了聚磷酸铵的粒度和溶解度。实验结果表明,制备聚磷酸铵的最佳反应条件为:n(磷酸氢二铵)∶n(五氧化二磷)∶n(尿素)=1∶1∶0.3,反应温度280~300℃,反应时间40m in,热处理温度250~280℃,热处理时间110m in。在此条件下制备的聚磷酸铵的平均聚合度大于600,平均粒径直径小于50μm,在水中的溶解度小于0.4g;XRD表征结果表明,所合成的物质为Ⅱ型聚磷酸铵。     

聚甲亚胺改性尼龙6复合材料的等温结晶动力学

采用差示扫描量热法（DSC）对聚甲亚胺（PAM）/尼龙6复合材料等温结晶过程进行了研究。结果表明，PAM的加入使得基体的结晶速率增大，尤其是当含量为5%时，半结晶期明显减少。研究还发现，该体系的等温结晶过程完全可以用Avrami方程来描述，各试样的Avrami指数均在2-3之间，表明Avrami指数，球晶生长方式基本不受聚甲亚胺加入的影响。基体中原位形成的聚甲胺微纤起到了诱导结晶的作用，使得基体的结晶速率加快，但随着微纤含量的增加，由于分散性能变差而使得诱导结晶的能力减弱，表现为结晶速率又有所降低。     

高分子表面活性剂对超声辐照下苯乙烯乳液聚合的影响

在超声辐照引发苯乙烯乳液聚合中加入一种新型的以羧甲基纤维素为基础的高分子表面活性剂(CMC—A9)，讨论了高分子表面活性剂对反应动力学的影响。实验表明，超声辐照下初级自由基并非由通常认为的高分子表面活性剂产生，而是十二烷基硫酸钠在超声辐照下断裂，产生自由基。通过对反应动力学的研究，发现超声辐照下乳液聚合机理不同于常规乳液聚合，聚合反应过程只有两个阶段，即加速期和减速期，不存在恒速期。加入CMC—A9高分子表面活性剂，可以在较短的时间内和较低的超声功率下达到较高的单体转化率。     

Experimental evidence of a relationship between monomer plasma residence time and carboxyl group retention in acrylic acid plasma polymers

Decreasing carboxyl retention in deposits from the glow region of an acrylic acid plasma was measured by X-ray photoelectron spectroscopy and chemical derivatisation as the collection distance from the monomer vapour inlet was increased. Volatilisation of plasma polymerised acrylic acid was detected after trifluoroethanol derivatisation; this is correlated with evaporation of low molecular weight components observed previously.