Synthesis of unsaturated polyester resins for large sized composites

A series of unsaturated polyesters based on phthalic anhydride (PHA), maleic anhydride (MA), ethylene glycol (EG), diethylene glycol (DG), triethylene glycol (TG), propylene glycol (PG), styrene (Sty) and acrylonitrile (AN) were prepared. The molecular weights of the prepared polyesters were determined by end-group analysis. The effect of the structure of the resin on its curing behavior has been investigated. On the basis of the experimental study, the following were concluded: (1) The maximum curing temperature (T_max) is related to the molecular weight of the glycol incorporated in these castings. In this context the T_max was found to decrease with increasing the molecular weight. Meanwhile the time to peak temperature t_max was increasing. (2) The higher the percentage of AN in the crosslinking monomer system, the slower a resin cures. (3) The values of T_max were found to be influenced to a large extent by the percentage of AN.     

Determination of styrene in olive oil by an automatic purge-and-trap system coupled to gas chromatography-mass spectrometry

Summary A new gas chromatographic method using an automatic purge-and-trap system coupled to a GC with mass selective detection to analyze styrene at the parts-per-trillions (ng kg^–1) level is described. The method shows a good sensitivity and the detection limit is 10 ng kg^–1 with a relative standard deviation (RSD) of 4.7% for 164 ng kg^–1 styrene in olive oil. This analytical method has been successfully applied to the analysis of styrene in extra-virgin olive oil from the European market.     

一步法合成苯乙烯催化剂表面积炭对活性的影响

应用ＥＳＲ，空气气氛下ＤＴＡ，氢气氛下ＴＰＳＲ，ＩＲ等技术手段，对反应后催化剂的积炭行为进行了研究。结果表明，反应后的催化剂表面不同程度地存在着不同类型和积炭，积炭是催化剂失活的主要原因。     

THE RING OPENING REACTION OF AN EPOXY COMPOUND ON THE TOP OF CHEMISORBED CYSTAMINE STUDIED BY THE SERS TECHNIQUE

Metal foils for Raman scattering were prepared by HNO_3 etching method. These foils werefound to exhibit a strong SERS effect and excellent thermal stability. SERS spectra of cystaminehave been taken to illustrate the usefulness of this sample preparation method in the studies ofchemisorption. The ring opening reactions of an epoxy compound have been observed on the topof chemisorbed cystamine on silver foils.     

苯乙烯和丙烯酸-β-羟乙酯不同温度的竞聚率测定

苯乙烯和丙烯酸 β 羟乙酯不同温度的竞聚率测定吴平平吴玉芳陆琛杨全兴韩哲文（华东理工大学材料科学研究所上海２００２３７）陈顺喜朱清仁（中科院中国科技大学结构分析开放实验室合肥２３００２６）关键词苯乙烯，丙烯酸 β 羟乙酯，共聚合，竞聚率丙烯酸 β?..     

Radical copolymerization of citraconic acid with styrene in dioxane solution

Styrene and citraconic acid (CA) were copolymerized in the dioxane solution ranging mole fraction of CA in feed from 0.1 to 0.9 at 70 °C. The terminal and penultimate models were used to fit the copolymer composition equation. Curve fitting, Mayo-Lewis, Joshi-Joshi, Fineman-Ross, Ezrielev-Brokhina-Roskin, Kellen-Tüd?s methods were used to solve the copolymer equation in terminal model. Besides these methods Solver in Excel 97 was used to solve copolymer equation in terminal and penultimate models of copolymerization. Experimental mole fractions of CA and those predicted from both models are agreed within the precision of the method used for the copolymer analysis, so the copolymer composition does not permit a definite choice of the adequate copolymerization model.     

π－烯丙基稀土配合物的合成、结构及其催化烯烃聚合反应机理的研究 Ⅲ．LiLn（π－C_3H_5）_4·nD催化异戊二烯和苯乙烯均聚合反应的研究

本文研究了ＬｉＬｎ（π－Ｃ_３Ｈ_５）_４·ｎＤ（Ｌｎ＝Ｌａ、Ｔｂ，ｎ＝３；Ｌｎ＝Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｇｄ、Ｅｒ，ｎ＝２；Ｌｎ＝Ｙ、Ｄｙ，ｎ＝２．５；Ｄ为二氧六环）催化异戊二烯和苯乙烯的均聚合反应．其中，钇配合物的催化活性为最高．聚异戊二烯顺式－１，４链节含量在４３－８１％．聚合体系内少量给电子体的加入使聚合物中３，４－链节含量高达８４％．所得聚苯乙烯为无规结构．     

Synthesis and characterization of perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl end-capped styrene oligomers

Styrene oligomers with perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl end-groups have been synthesized with moderate to high yields (52-97%) via radical oligomerization by using perfluoro[2-(2-fluorosulfonyl)ethoxy]propyonyl peroxide (PPP) at various reactant ratios of styrene over PPP (80, 160, 240, 300, 360 and 420) and different temperatures (33, 37 and 42 °C), and characterized by FTIR, ¹H NMR and ¹⁹F NMR. The molecular weight of the oligomers measured by gel permeation chromatography (GPC) is dependent on the reactant ratio and reaction temperature. The polydispersity of the oligomers varies from 1.99 to 3.30. The oligomer obtained at the reactant ratio of 300 has the maximum yield (97%) and much broader polydispersity (3.30). The contact angles of water, θ_H2O, on the oligomer films are much bigger than that of polystyrene (PS). The glass transition temperature of the oligomers, T_g, increases with the increase of molecular weight and is lower than that of the parent polymer.     

1,3-二烯基-1,1,3,3-四甲基二硅氧烷/苯乙烯共聚合的环化率与竞聚率

对１３０℃下１，３ 二烯基 １，１，３，３ 四甲基二硅氧烷（ＤＶＤＳ）／苯乙烯（Ｓｔ）的溶液环化共聚合动力学进行了研究．根据低转化率（＜１０％）的共聚物组成及环状结构比例，通过参数估计方法，求得环化率与竞聚率，分别为ｒ１＝０１０２、ｒ２＝３４８、ｒｃ＝００２１０、Ｋｃ＝３８１ｍｏｌ／Ｌ、Ｋ′ｃ＝０３８９ｍｏｌ／Ｌ，同时得到它们９５％置信概率的联合置信区间及其交互影响的联合置信区间．表明ＤＶＤＳ的反应活性较Ｓｔ低，其非环状结构自由基具有较强的分子内环化反应能力；环的位阻效应使环状结构ＤＶＤＳ自由基的活性低于其非环状结构自由基．     

钴膦簇合物的催化环丙烷化反应

本文首次利用碳基钴簇合物ＰｈＰＣｏ_３（ＣＯ）_９催化剂，在常压和－２０℃－０℃，用苯乙烯和重氮乙酸乙酯进行环丙烷化反应，合成了菊酸酯，重氮乙酸乙酯可全部转化，酯的选择性可达８５％。产物经减压分馏后，由ＩＲ和￣１ＨＮＭＲ分析，确证了产物为菊酸酯，表明了羰基钴簇合物对苯乙烯的环丙烷化反应有良好的催化性能，为四面体异核簇合物用于不对称催化反应打下了基础。