混凝土防水材料辛基硅烷的合成工艺研究

以1-辛烯和三乙氧基氢硅烷为原料,在Karetedt催化剂及酸促进剂作用下,进行硅氢加成反应合成正辛基三乙氧基硅烷,研究了反应温度、滴加方式、催化剂用量、促进剂用量、滴加时间等工艺条件对原料烯烃异构化及产品收率的影响。利用核磁共振(1HNMR)对烯烃异构体和目标产品正辛基三乙氧基硅烷进行结构鉴定,利用气相色谱对反应后液体进行进一步定性、定量检测。结果表明:以三乙氧基氢硅烷为滴加剂,反应温度在90~100℃之间,催化剂用量0.000 15%(质量分数)~0.000 20%,促进剂用量为0.15%~0.20%,滴加时间1.5 h为正辛基三乙氧基硅烷合成的最佳工艺条件。在此条件下,反应后液体中异构烯烃含量为1.34%,产品含量为92.48%。     

具有多齿配位基的硅单体

通过含多齿配位基的烯烃与三乙氧基硅烷的硅氢加成反应、或γ-巯丙基三甲氧基硅烷与β-氯乙基硫醚的缩合反应,合成了5种新型具有多齿配位基的硅单体。     

三硅氧烷咪唑离子液体表面活性剂的合成与表面活性

以氯丙基甲基二甲氧基硅烷和六甲基二硅氧烷为原料,在浓硫酸催化下合成了氯丙基三硅氧烷,再与1-甲基咪唑进行季铵化反应,制备了三硅氧烷咪唑离子液体表面活性剂.用傅里叶红外光谱仪以及氢谱和碳谱核磁共振仪表征了产物的结构;并对其临界胶束浓度(cmc)及表面张力(γ)进行了测定.结果表明,与长链烷基咪唑类离子液体表面活性剂相比,三硅氧烷咪唑离子液体表面活性剂具有更好的表面活性,其cmc为15.5 mmol/L,γcmc为24.0 mN/m.     

聚γ—巯丙基硅氧烷铂（Ⅱ）配合物的合成及其催化硅氢化性能

γ－巯丙基三乙氧基硅烷用气相法二氧化硅固载,再与氯亚铂酸钾作用,合成了聚γ－巯丙基奎氧烷铂（Ⅱ）配合物。研究了该了该梧全物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性。     

正辛基三乙氧基硅烷的合成

在催化剂存在下,利用正辛烯与三乙氧基氢硅烷进行硅氢加成反应制备正辛基三乙氧基硅烷.采用气相色谱-质谱(GC-MS)法对正辛基三乙氧基硅烷的结构进行了表征,考察了滴加方式、原料配比、反应温度以及反应时间对反应的影响.较佳的反应条件为:正辛烯和三乙氧基氢硅烷以1.05:1的量之比投料,采用滴加三乙氧基氢硅烷的方式反应,反应...     

4A分子筛固载铂催化剂催化乙炔硅氢加成反应

研究了4A分子筛固载铂催化剂的制备及其催化乙炔与三乙氧基硅烷硅氢加成反应的反应规律,考察了反应温度、原料配比、催化剂铂含量、乙炔流量等对反应的影响.结果说明4A分子筛固载铂催化剂对乙炔与三乙氧基硅烷硅氢加成反应具有较好的催化活性,并且反应条件温和,催化剂回收利用3次仍具有较高的活性.     

聚乙二醇双咪唑型离子液体促进RhCl_3催化烯烃硅氢加成反应的研究

一系列聚乙二醇双咪唑型离子液体被合成和表征,并应用于Rh Cl3催化烯烃硅氢加成反应中。考察了Rh Cl3用量、离子液体用量、反应温度和反应时间对催化结果的影响。在低温、无溶剂条件下,该催化剂体系表现出较高的转化率和良好的选择性。     

十烷基三乙氧基硅烷

正华南理工大学的吴忠喜等人将1-十碳烯(C10)和三乙氧基硅烷(TES)在铂催化剂存在下进行硅氢加成反应,合成了十烷基三乙氧基硅烷。较佳工艺为:以铂-四甲基二乙烯基二硅氧烷为催化剂且n(Pt)∶n(TES)=1.2×10-5∶1,n(C10)∶n(TES)为0.95∶1,在110℃下反应3 h;在此条件下,十烷基三乙氧基硅烷的产率可     

烯丙基硅(氧)烷铂配合物硅氢加成催化剂

南京大学的张墩明等以二甲基二氯硅烷、甲基三氯硅烷、二苯基二氯硅烷、苯基三氯硅烷、1 ,3-二氯 -四甲基二硅氧烷和四氯化硅、烯丙基氯等为原料 ,通过格氏反应制得 5种烯丙基硅烷化合物和 1 ,3-二烯丙基四甲基二硅氧烷 ,它们再与氯铂酸反应制成了相应的烯丙基硅(氧 )烷铂配合物。配合物可用做硅氢加成反应催化剂。讨论了几种铂配合物催化剂对含氢硅油与乙烯基硅橡胶的加成反应活性。烯丙基硅(氧)烷铂配合物硅氢加成催化剂     

多烷基咪唑离子液体的合成及性能比较

以咪唑或1,2-二甲基咪唑和卤代烷为原料,合成了4种多烷基咪唑类离子液体,以及6种1,3-二丁基咪唑和1-丁基-3-乙基咪唑类离子液体,产率较高。产物结构经核磁共振氢谱进行了确认。测定了产物水溶液的pH和不同浓度下的电导率,研究了烷基对离子液体酸性的影响,以及不同阴离子或烷基链长度对电导率的影响。测定了产物的吸湿性,结果表明,多烷基咪唑六氟磷酸盐离子液体具有较低的吸湿性。     

甲苯/酸性离子液体两相中顺酐选择性加氢生成四氢呋喃的研究

在甲苯/离子液体两相催化体系中,以三苯基膦和三氯化钌活化生成的配合物为催化剂,研究了顺酐选择性加氢生成四氢呋喃的反应,考察了离子液体、反应时间、反应温度、反应压力、顺酐与催化剂物质的量比以及离子液体用量对加氢反应的影响,同时考察了离子液体的循环使用。在453 K、12 h、4 MPa和n(PPh₃)∶n(RuCl₃)＝3∶1的条件下,反应的转化率和选择性分别为100%和962%。由于催化剂“负载”于离子液体中且产物不溶于离子液体,通过简单的相分离即可分离催化剂和产物。离子液体催化体系重复使用5次后,其催化活性基本不变。     

SO3H-功能化季铵盐离子液体催化酯交换制备生物柴油

采用两步合成法制备了4种SO3H-功能化季铵盐离子液体,红外与核磁共振光谱表征结果表明,其结构符合理论结构特点. 热稳定性分析表明,其分解温度都在200℃以上,均可作为制备生物柴油的催化剂. 将这4种离子液体用于催化制备生物柴油,其催化活性主要与其阴离子的结构有关,[n-But3N(CH2)3SO3H][CH3SO3]的催化活性最好. 甲醇:三油酸甘油酯摩尔比为12:1、催化剂用量7%(w)、在65℃下反应24 h时,油酸甲酯产率最高(89.65%). 催化剂重复使用性能良好.     

Ion exchange characteristics of rhodium and ruthenium from a simulated radioactive liquid waste

Radioactive high-level liquid wastes contain significant quantities of platinum group metals (PGM) such as palladium [Pd(II)], rhodium [Rh(III)] and ruthenium [Ru(III)]. The PGM are produced as fission products in a nuclear reactor. In this study, batch and column experiments were carried out to investigate the ion exchange characteristics of Rh(III) and Ru(III) including the effects of the ionic group of ion exchangers, solution temperature, and the concentration of nitric acid by various ion exchangers such as IRN 78 and Dowex 1x 8; the elution characteristics of Rh(III) and Ru(III) by various eluents were also investigated. Anion exchangers such as Dowex 1x 8 with the ionic group of quaternary methyl ammonium had a higher capacity than anion exchanger such as IRN 78 with amine group for the adsorption of Rh(III) and Ru(III) from a simulated liquid waste. The optimal nitric acid concentration for the adsorption of Rh(III) and Ru(III) by anion exchangers was shown to be about 3 M and 2–3 M, respectively.     

碱性离子液体1-乙基-3-甲基咪唑磷酸二乙酯盐在Knoevenagel反应中的应用

考察了碱性离子液体1-乙基-3-甲基咪唑磷酸二乙酯盐{[Em im]+[(EtO)2(PO)O]-}催化一系列醛与活性亚甲基类化合物的Knoevenagel反应,比较了该离子液体在有溶剂存在及无溶剂条件下的催化性能。结果表明,该离子液体在乙醇作溶剂条件下对芳香醛的反应具有较高的催化活性,采用摩尔分数为20%的离子液体来催化该反应,于室温反应即可顺利完成,产率达73.2%~97%,生成相应的取代烯烃化合物。在无溶剂条件下采取机械研磨的方法进行反应,该离子液体表现出更高的催化活性,采用摩尔分数为10%的离子液体进行反应,在1~10 m in即可使产率达90%以上,所得产物均为E式构型。而且在无溶剂条件下,不仅可催化芳香醛的反应,亦可催化脂肪醛的反应。所用离子液体可重复使用,第5次使用时产率仍能达到85.9%。     

混合C_8烯烃氢甲酰化反应的实验研究

对几种铑膦络合物催化混合 C8烯烃氢甲酰化反应作了实验研究 ,结果表明 ,在一定反应条件下 ,[Rh( CH3COO) 2 ]2 、Rh( CO) PPh3( acac)和 Rh6 ( CO) 16 均是有效的催化剂前体。配体、铑的浓度及溶剂对催化体系性能影响的实验证明 ,外加 OPPh3、选用适量 Rh浓度及加入二乙二醇二甲醚或四乙二醇二甲醚等溶剂对 C8烯烃氢甲酰化反应生成 C9醛是有利的。实验表明 ,对于 [Rh( CH3COO) 2 ]2 - OPPh3催化体系在 1 40℃及 1 0 .5MPa反应条件下 ,混合 C8烯烃氢甲酰化反应生成 C9醛的收率可达 90 %以上。     

Process Variables of the Esterification Reaction of 3‐Pentadecylphenol and Acryloyl Chloride Catalyzed by an Ionic Liquid

An efficient method was investigated for the synthesis of 3‐pentadecylphenyl acrylate (PDPA) via one‐pot reaction of esterification in the presence of an ionic liquid as catalyst. In order to understand the esterification reaction process, a mathematical relationship between the yield of esterification and the process variables was established by employing central composite design. The maximum yield of esterification of 3‐pentadecylphenol (PDP) and acryloyl chloride (AC) catalyzed by imidazole ionic liquid was found to be 85 %. A statistical model predicted that the highest esterification reaction yield would be > 88 % under optimized reaction conditions. The predicted values for optimum process conditions thus obtained were in agreement with the experimental values, thereby indicating the suitability of the model.     

[Cnmim]Br/FeCl3型离子液体萃取脱除二苯并噻吩

合成了6种咪唑型离子液体[C_3-8mim]Br/FeCl₃,采用红外光谱和拉曼光谱对其进行表征,并考察了离子液体对二苯并噻吩的萃取脱除效果。结果发现,[C₃mim]Br/FeCl₃的萃取脱硫效果最佳,升高温度和增大剂油比均有利于脱硫率的提高,剂油比1:1(体积比)时,萃取时间达到12 min就可使脱硫率高达92%。且萃取反应完成后,离子液体不做处理继续重复使用,重复使用5次,脱硫率可以达到60%。     

甲苯稀释对AlCl3-EMIC型离子液体电镀铝工艺氢脆性的影响

采用甲苯作为AlCl3-EMIC(1-乙基-3-甲基咪唑)型离子液体的稀释剂,其中纯态离子液体由物质的量比为2∶1的无水AlCl3和EMIC组成。对比了纯态和按稀释剂与离子液体体积比为1∶1稀释后电镀铝的外观、微观形貌和氢脆性。结果表明,采用甲苯稀释离子液体虽然可以降低镀液的黏度,改善镀层外观和微观形貌,但对离子液体电镀铝工艺的氢脆性有负面影响。     

Effect of Rh loading on the performance of Rh/Al2O3 for methane partial oxidation to synthesis gas

Catalytic performance for partial oxidation of methane (POM) to synthesis gas was studied over the Rh/Al₂O₃ catalysts with Rh loadings between 0.1 and 3 wt%. It was found that the ignition temperature of POM reaction increased with the decreasing of the Rh loadings in the catalysts. For the POM reaction over the catalysts with high (≥1 wt%) Rh loadings, steady-state reactivity was observed. For the reaction over the catalysts with low (≤0.25 wt%) Rh loadings, however, oscillations in CH₄ and reaction products (CO, H₂, and CO₂) were observed. Comparative studies using H₂-TPR, O₂-TPD and high temperature in situ Raman spectroscopy techniques were carried out in order to elucidate the relation between the redox property of the Rh species in the Rh/Al₂O₃ with different Rh loadings and the performance of the catalysts for the reaction. Three kinds of oxidized rhodium species, i.e. the rhodium oxide species insignificantly affected by the support (RhO_x), that intimately interacting with the Al₂O₃ surface (RhⁱO_x) and the Rh(AlO₂)_y species formed by diffusion of rhodium oxides in to sublayers of Al₂O₃ [C.P. Hwang, C.T. Yeh, Q.M. Zhu, Catal. Today, 51 (1999) 93.], were identified by H₂-TPR and O₂-TPD experiments. Among them, the first two species can be easily reduced by H₂ at temperature below 350 °C, while the last one can only be reduced by H₂ at temperature above 500 °C. The ignition temperatures of POM reaction over the catalysts are closely related to the temperature at which most of the RhO_x and RhⁱO_x species can be reduced by CH₄ in the reaction mixture. Compared to the Rh/Al₂O₃ with high Rh loadings, the catalysts with low Rh loadings contain more RhⁱO_x species which possess stronger RhO bond strength and are more difficult to be reduced than RhO_x by the reaction mixture. Higher temperature is therefore required to ignite the POM reaction over the catalysts with lower Rh loadings. The oscillation during the POM reaction over the Rh/Al₂O₃ with low Rh loadings can be related to the behaviour of Rh(AlO₂)_y species in the catalyst switching cyclically from the oxidized state to the reduced state during the reaction.     

富氧条件下Rh/Co_3O_4催化剂对C_3H_6还原NO性能的影响

采用液相沉淀法制备Co3O4氧化物,并以其为载体制备负载型Rh催化剂。考察不同焙烧温度制备的载体和催化剂的结构、织构、氧化还原性能及其对C3H6催化还原NO性能的影响。结果发现,经600℃焙烧的载体制备的Rh/Co3O4催化剂中Rh与Co3O4的相互作用较强,促进对N—O键的削弱作用,提高对C3H6还原NO的还原能力。在相同实验条件下,当体系中C3H6为500×10-6、NO为500×10-6和O2体积分数为5%时,NO转化率50%,催化性能优于Rh/Al2O3催化剂。