Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Study of the influence of reaction conditions on the degree of substitution,intrinsic viscosity,and yield of oxidized cellulose acetate by factorial experimental design

A half‐fraction, two‐level, four‐factor factorial experimental design was used to study the effects of the acetic anhydride concentration, reaction temperature, reaction time, and sulfuric acid concentration on the degree of substitution, intrinsic viscosity, and yield of oxidized cellulose acetate (OCA). Oxidized cellulose containing 20% (w/w) carboxylic acid was used as the starting material. The data were fitted by multiple regression analysis with SAS software. The correlation coefficients obtained from plots of the predicted and observed values for the degree of substitution, intrinsic viscosity, and yield were 0.985, 0.993, and 0.991, respectively. Residual normal plots of the regression models showed a linear relationship. Lenth and main‐factor‐effect plots revealed an increase in the degree of substitution of OCA with an increasing concentration of acetic anhydride. The latter had no effect on the intrinsic viscosity and yield of OCA. An increase in the reaction temperature led to an increase in the degree of substitution and a decrease in the intrinsic viscosity and yield of OCA. The influence of the reaction time on the degree of substitution and intrinsic viscosity followed a trend similar to that observed with the reaction temperature, but the yield of OCA was unaffected. Increasing the concentration of sulfuric acid reduced the degree of substitution, intrinsic viscosity, and yield of OCA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 696–705, 2005     

From surface science to catalysis: Surface “explosions” observed on Rh crystals and supported catalysts

Phenomena called surface explosions have been reported for decomposition reactions on single crystals, and have been identified by the use of desorption methods. In particular, in TPD, they are manifested by extremely narrow peaks (as little as 3 K in width) and a desorption rate which increases with time in isothermal experiments. In this paper we report such observations for acetate species on Rh single crystals, but extend this to show for the first time that such effects are not restricted to single crystal/UHV experiments, but can also be found on a Rh/Al₂O₃ catalyst under ambient pressure conditions. These reactions can be classified as second order autocatalytic surface processes, where free surface Rh sites are an essential component of the reaction. It is shown that coadsorbed adatoms are also essential for such explosions to be seen and their role is proposed to be that of a template layer acting to order the acetate in self-poisoning configurations.     

Effect of Water on the Partial Oxidation of Propane to Acrylic and Acetic Acids on Mo-V-Sb-Nb Mixed Oxides

It is shown that the major effect of water in the oxidation of propane to acrylic and acetic acids on Mo₁V_0.3Sb_0.25Nb_0.08O _n catalysts is to stabilise the active sites and increase the rates of formation of both acids. The usual effect of favoring desorption of the products is considered to be secondary.     

In situ esterification of rice bran oil with methanol and ethanol

In situ esterifications of high-acidity rice bran oil with methanol and ethanol and with sulfuric acid as catalyst were investigated. In the esterification with methanol, all free fatty acids (FFA) dissolved in methanol were interesterified within 15 min, and it was possible to obtain nearly pure methyl esters. The amount of methyl esters obtained from a given rice bran was dependent on the FFA content of the rice bran oil. In the esterification with ethanol, it was not possible to obtain pure esters as in methanol esterification, because the solubilities of oil components in ethanol were much higher than those in methanol.     

Surface disposition and stability of pest-interactive,trichome-exuded diterpenes and sucrose esters of tobacco

The precise physical location of trichome-exudate biochemicals on the plant surface is undoubtedly important in plant-pest interactions, perhaps particularly those involving fungal and bacterial pathogens that invade the plant through the epidermal layer. The chemical stability of exuded compounds is also important in this regard. Here we have studied these two aspects of trichome biology using the highly exuded tobacco line,Nicotiana tabacum, T.I. 1068. Particularly under high relative humidity growth conditions, sucrose esters (SE) were found to migrate from the exudate droplet around the gland down the trichome stalk to the epidermal cells below. Six days after labeling leaf midveins on plants grown in a high humidity environment, 29 and 71% of label found in SE were recovered with trichome glands and below gland regions, respectively. Corresponding disposition in the moderate humidity environment was 40 and 60%, respectively. Migration of less polar duvatrienediols (DVT) was less marked. Staining of SE with rhodamine B showed the occurrence of more extensive and physically different migration in the high humidity versus moderate humidity case. Both SE and DVT were stable between six and 18 days postlabeling, the period encompassing the time of maximum exudate formation through the beginning of tissue senescence. Our results suggest that even under conditions that avoid mechanical disturbance of tissue, SE and DVT are chemically stable, at least until senescence, and appear to migrate from the gland region to the epidermal surface, apparently according to their relative polarity.     

微波辐射下NKC-9树脂催化合成1-萘乙酸甲酯

以NKC-9阳离子交换树脂为催化剂,在微波条件下用1-萘乙酸和甲醇合成1-萘乙酸甲酯.最佳合成条件为:醇酸摩尔比为14:1,催化剂为1-萘乙酸的80%,微波辐射时间为15分钟,微波功率为600瓦,产率为80.48%.     

苹果梨醋发酵过程中醋酸发酵条件的优化

以甲酚紫培养基中加入乙醇作为分离培养基,从5种水果样品中分离得到20种醋酸菌,然后通过产酸量的测定,筛选出了一株产醋酸度高的醋酸菌AAB13.探讨了乙醇浓度、菌株接种量、发酵液有效体积对醋酸发酵的影响,并在优化的条件下制备了苹果梨醋.     

新型蔗糖基聚羧酸高效减水剂的合成与性能

以自制甲基丙烯酸蔗糖酯（MASE）、丙烯酸（AA）、甲基丙烯酸（MAA）、烯丙基磺酸钠和烯丙基聚乙二醇（A PEG ）为原料,以过硫酸钾为引发剂,自由基共聚法合成蔗糖基聚羧酸高效减水剂。研究了反应时间、蔗糖酯含量及引发剂用量对蔗糖基聚羧酸高效减水剂性能的影响。并通过流动度测试、红外光谱表征及黏度对减水剂的结构与性能进行了分析与比较。各组分物质的量nAA ：nMAA ：nSAS ：nAPEG ：nMASE ＝3∶1∶2∶1∶0．2,MASE含量为4．9wt．％,引发剂为单体用量1．9wt．％,反应时间为5h时合成的减水剂性能最好。在水灰比为0．29,折固掺量为0．3w t ．％,水泥净浆流动度达到340mm。     

羰基合成醋酐反应条件的实验研究

对羰基液相合成醋酐反应过程中受温度、压力、停留时间等反应条件的影响进行实验研究,通过对实验数据的分析,确定优化条件为:反应时间15~20 min,反应压力(10~15)×105Pa,反应温度290~300 K,催化剂浓度40~45 g/L,搅拌速率10~12 n/min,为工艺的工业化放大提供了依据。