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     

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     

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。     

碳黑对苯乙烯自由基聚合反应影响的研究

研究了碳黑对苯乙烯单体聚合物反应的影响，结果表明，用过氧化苯甲酰作引发剂，普通碳黑子对苯乙烯的聚合有强烈的阻聚作用，而用偶氮二异丁腈引发聚合物时，普通碳黑的阻聚性很小，当时碳黑进行接枝处理后，接枝碳黑对苯乙烯自由基聚合的影响程度与接枝方法有关，其中过氧化苯甲酰 自由基枝枝碳黑的聚性变化较大。     

Kinetics of two-step anionic polymerization

This article deals with the kinetics of two-step anionic polymerization by way of a non-steady state method. Several molecular parameters can be evaluated using the formulae developed. A bimodal molecular weight distribution function for the resulting polymer is derived from the set of kinetic differential equations, which is in agreement with the experimental data reported.     

聚合物载体－稀土金属络合物的研究 ⅩⅢ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］的结构与其稀土金属络合物催化丁二烯聚合的活性

从测得的竞聚率计算了单体链节在聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］（ＰＳＭ）中的序列分布。苯乙烯（Ｓ）或甲基丙烯酸β（甲基亚硫酰基）乙酯（Ｍ）的长序列的概率随着ＰＳＭ中相应单体含量的增加而增加。对于Ｓ和Ｍ摩尔分数大致相等的ＰＳＭ，单体链节的长序列分布函数值相接近。用与此结构相近的ＰＳＭ合成的稀土金属络合物，其催化活性不佳。在Ｍ短序列分布和Ｓ长序列分布较高的情况下，络合物的催化活性最好。所得聚丁二烯的微观结构与ＰＳＭ中单体单元的分布无关。     

新型硅蜡乳液的制备

将蜂蜡用复合乳化剂乳化时加入自制的乳化助剂，制得稳定的蜡乳液，将该乳液与羟基蛙油乳液复配，制得乳白色略带蓝光硅蜡乳液，该硅蜡乳液用于绵羊服装革作顶层手感改善剂，除了获得油润的蜡感和滑爽感之外，还使成革具有抗菌和抗静电作用。     

Synthesis and properties of peroxy derivatives of epoxy resins based on Bisphenol A: Effects of the presence of boron trifluoride ethereate

Oligomers containing peroxy groups have been synthesized on the basis of epoxides reacting with tert–butylhydroperoxide in the presence of boron trifluoride etherate. Dependence of reaction rates upon the quantity of catalyst, temperature and also nature of hydroperoxide has been investigated: A kinetic equation for the process has been formulated and also a kinetic scheme for the reaction taking into account the presence of boron trifluoride etherate is proposed. Structures of the synthesized peroxy oligomers have been confirmed by IR- and NMR-spectroscopy. The reaction initiating properties of the oligomers so synthesized were studied using as the example the styrene polymerization reaction. Electronic Publication     

PEG20000中试放大的工艺研究

在一定温度和催化剂作用下 ,分别利用本体聚合和溶剂聚合的方法 ,在 1L、10 0L不锈钢高压反应釜中合成了相对分子质量为 2 0 0 0 0的聚乙二醇 ,并讨论了聚合反应机理 ,研究了催化剂用量、反应温度、反应时间对聚合反应的影响。经过红外、核磁共振、凝胶色谱、化学分析等方法对产物进行了表征。