Epoxy-amine multimethacrylic prepolymers,kinetic and structural studies

Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc.     

阳离子无皂含氟丙烯酸酯的合成与表面性能

在合成甲基丙烯酸全氟辛酰氧基乙酯(FA)基础上,用半连续法制备了无皂阳离子含氟丙烯酸酯乳液。当乳液的粒径在100~200 nm、ζ电位大于40 mV时,乳液较稳定。阳离子亲水单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)在含氟丙烯酸酯中质量分数为0.10~0.18、固含量小于20%时乳液的稳定性好,且随DMC含量的增加稳定性提高;含氟丙烯酸酯乳胶膜的附着力与耐磨性好,乳胶膜的透湿率随DMC的增加而增加。随热处理温度的提高,膜表面自由能下降;经160℃热处理后膜发生了交联,表面自由能为18 mN/m,与聚四氟乙烯(PTFE)的表面能相近,DMC含量对膜表面自由能影响不大。XPS分析也表明膜表面氟含量随热处理温度的提高而增加。     

A mild hydrolysis of esters mediated by lithium salts

When treated with amine bases such as triethylamine and various lithium salts in wet solvents, esters are efficiently hydrolyzed to the corresponding acids in good yields. Esters incorporating an α- or β-heteroatom with respect to the ester carbonyl group are hydrolyzed rapidly even at room temperature. To further demonstrate the usefulness of this method, one example is provided where hydrolysis of acetylated camphorsultam is mediated by LiBr.     

Translucent nanolatexes through emulsion polymerisation of ethyl acrylate

Turbid emulsion systems of ethylacrylate/sodium dodecyl sulphate/water with monomer to surfactant (M/S) ratios 10 and 40 were transformed into stable transparent/translucent nanolatexes through emulsion polymerisation using potassium persulphate as an initiator. The latex particle size was observed to be similar to that obtained by true microemulsion polymerisation where M/S ratio is one. The kinetic plots exhibited two intervals upto M/S ratios 10. AIBN initiated systems showed separation of two phases for the M/S ratio ?10. M/S ratios were varied from 1 to 54 for the comparative study of polymerisation in emulsion and microemulsion media. Gel effect dominance was observed around 40-60% conversion for the microemulsion polymerisation of ethylacrylate. Only one chain per particle was observed for microemulsion system with M/S ratio 1 and three to four chains per particle were observed for the systems with M/S ratios 10 and 40. Unlike M/S=1 system, higher dependency of polymerisation rate on initiator concentration was observed for the systems with M/S=10 and 40. A possible mechanism for such a transformation has been proposed.     

Effects of Strong Ion‐Pairing on the Electrochemical Reduction of Cyclooctatetraene in Tetrahydrofuran in the Presence of Lithium Ion. Peak Coalescence Does Not Imply Potential Inversion

The first study of the voltammetric reduction of cyclooctatetraene (COT) in tetrahydrofuran (THF) in the presence of lithium ion is reported. A single wave is observed at ?2.23 V vs. Ag/0.1 M AgNO₃. Density functional calculations have been carried out on a variety of COT/Li/THF species in order to clarify the nature and role of ion pairing in this system. The dominant species in solution are the COT/Li/(THF)₂ anion radical and the COT/Li₂/(THF)₄ dianion. Computer simulations have been carried out to further understand the effects of ion pairing on the reduction. The simulations show that coalescence of two waves into one can occur in the presence of strong ion pairing even when the second reduction potential is negative of the first.     

Synthesis and phase transition of Li-Mn-O spinels with high Li/Mn ratio by thermo-decomposition of LiMnC2O4(Ac)

LiMnC₂O₄(Ac) precursor in which Li⁺ and Mn²⁺ were amalgamated in one molecule was prepared by solid-state reaction at room-temperature using manganese acetate, lithium hydroxide and oxalic acid as raw materials. By thermo-decomposition of LiMnC₂O₄(Ac) at various temperatures, a series of Li_1+y[Mn_2−xLi_x]_16dO₄ spinels were prepared with Li₂MnO₃ as impurities. The structure and phase transition of these spinels were investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. Results revealed that the Li-Mn-O spinels with high Li/Mn ratio were unstable at high temperature, and the phase transition was associated with the transfer of Li⁺ from octahedral 16c sites to 16d sites. With the sintering temperature increasing from 450 to 850 °C, the phase structure varied from lithiated-spinel Li₂Mn₂O₄ to Li₄Mn₅O₁₂-like to LiMn₂O₄-like and finally to rock-salt LiMnO₂-like. A way of determining x with average oxidation state of Mn and the content of Li₂MnO₃ was also demonstrated.     

Degradation of poly(acrylates) under SF5+ primary ion bombardment studied using time‐of‐flight secondary ion mass spectrometry. 1. Effect of main chain and pendant methyl groups

Polyatomic primary ions have been applied recently to the depth profiling of organic materials by secondary ion mass spectrometry (SIMS). Polyatomic primary ions offer low penetration depth and high damage removal rates in some polymers, but the relationship between polymer chemistry and degradation under polyatomic primary ion bombardment has not been studied systematically. In this study, positive and negative ion time‐of‐flight SIMS (ToF‐SIMS) was used to measure the damage of ～100 nm thick spin‐cast poly(methyl methacrylate) (PMMA), poly(methyl acrylate) (PMA) and poly(methacrylic acid) (PMAA), films under extended (～2 × 10¹⁴ ions cm^?2) 5 keV SF₅⁺ bombardment. These polymers were compared to determine the effect of the main chain and pendant methyl groups on their degradation under SF₅⁺ bombardment. The sputter rate of PMMA was approximately twice that of PMA or PMAA and the rate of damage accumulation was higher for PMA and PMAA than PMMA, suggesting that the main chain and pendant methyl groups played an important role in the degradation of these polymers under SF₅⁺ bombardment. These results are consistent with the literature on the thermal and radiation‐induced degradation of these polymers, which show that removal of the main chain or pendant methyl groups reduces the rate of depolymerization and increases the rate of intra‐ or intermolecular cross‐linking. Copyright © 2004 John Wiley & Sons, Ltd.     

手性丙烯酸酯液晶原位光聚合反应

手性丙烯酸酯液晶原位光聚合反应何流，张树范，金顺子，漆宗能，王佛松（中国科学院化学研究所北京１０００８０）关键词手性丙烯酸酯，原位光聚合，双折射，近晶相手性侧链液晶高分子显示近晶Ｓ！相，具有铁电性，在光电功能材料和非线性光学材料方面有潜在的应用前景’...     

DABCO-catalyzed reactions of hydrazones with activated olefins

This paper describes several highly efficient DABCO-catalyzed aza-Michael addition reactions of hydrazones to activated olefins. In most cases, these aza-Michael addition reactions gave the corresponding products in high yields under mild conditions. The plausible reaction mechanism is discussed on the basis of deuterium labeling experiments. Upon treatment with HCl, the corresponding cyclized products can be obtained in high yields from the Michael addition products.     

氧化-还原低温引发甲基丙烯酸甲酯/丙烯酸丁酯超浓乳液聚合研究

以乳化剂十二烷基硫酸钠 (SDS)和共乳化剂十六烷醇 (HD)作为复合乳化体系 ,过氧化二苯甲酰(BPO)和N ,N 二甲基苯胺 (DMA)作为氧化还原引发体系 ,甲基丙烯酸甲酯 丙烯酸丁酯 (MMA BA)作为混合单体 ,制备了分散相占 83 %以上的稳定的超浓乳液 ,然后在低温下引发聚合 .探讨了引发剂浓度、氧化剂与还原剂的摩尔比、乳化剂的浓度、液膜增强剂的种类、聚合温度等因素对聚合稳定性和聚合速率的影响 ,测定并计算得到了聚合速率的公式 ;用激光散射粒度分布仪测定了聚合物乳胶粒子的大小及粒径分布 ,用透射电子显微镜观察了聚合物乳胶粒的形态 ,讨论了乳化剂浓度、聚合温度等对乳胶粒形态、大小的影响