Amine/anhydride reaction versus amide/anhydride reaction in polyamide/anhydride carriers

Polyamide 6 (PA6) and poly(metaxylene adipamide) (PAmXD6) were blended in a batch mixer with anhydrides such as phthalic anhydride, n-octadecyl succinic anhydride, and anhydride-grafted ethylene propylene rubber. The melt viscosity, the solution viscosity, and chain end concentration were studied during the mixing. PA was first mixed 5 min to get an homogeneous melt prior to the anhydride addition. The introduction of the anhydride to the molten polyamide resulted in large decreases of melt and solution viscosities and of amine chain end concentrations. The anhydride units react with amine chain ends to form imide groups. The resulting low amine chain end concentration causes hydrolysis reaction to maintain the condensation equilibrium. As a consequence an increased carboxylic chain end concentration is observed. The imide concentration was studied by IR. It was shown that when most of the amine chain ends are consumed, the remaining anhydride reacts with amino groups formed by polyamide hydrolysis. © 1995 John Wiley & Sons, Inc.     

Determination of Semicarbazide-Sensitive Amine Oxidase Activity in Blood Plasma by a Light Scattering Technique

A novel method for the determination of semicarbazide-sensitive amine oxidase (SSAO) activity in blood plasma has been developed. The method was based on the change of light scattering (LS) intensity resulting from the derivative product of the interaction of 2,4-dinitrophenylhydrazine (DNPH) with benzaldehyde produced by catalyzing of SSAO to benzylamine. In Britton-Robinson (B-R) buffer solution, the intensity of system's LS at 514.6 nm was significantly enhanced and was directly proportional to the concentration of benzaldehyde. In this method, SSAO enzyme activity is defined as the concentration of benzaldehyde (nmol) formed per mL plasma per hour. The range of determination of SSAO enzyme activity was 6.40 × 10^?3 ?0.340 nmol mL^?1 h^?1 with a detection limit of 1.92 × 10^?3 nmol mL^?1 h^?1. The relative standard deviation was 2.8–4.1% and the average recovery was 67.9% (n = 6).     

三丁胺胺化强碱性阴离子交换树脂催化合成羧酸苄酯

用组合化学方法筛选出的对无外加碱条件下的亲核取代催化活性最高的聚合物季铵盐-三丁胺胺化强碱性阴离子交换树脂为相转移催化剂,催化合成了乙酸苄酯、丙酸苄酯、丁酸苄酯、戊酸苄酯等羧酸苄酯。讨论了各种反应条件对合成丙酸苄酯的产率的影响,并对传统合成方法进行了改进。在优化反应条件下,反应产率接近100%。     

伯胺N~1~9~2~3萃取硫酸铀酰的机理研究

研究了伯胺N~1~9~2~3的正庚烷溶液从硫酸介质中萃取硫酸铀酰的机理。认为伯胺N~1~9~2~3的硫酸盐在有机相中形成了反向胶束(或胶团),并由红外光谱和透射电镜佐证。伯胺N~1~9~2~3和铀酰形成的萃合物主要存在于反向胶束准相中。可以较好地解释用斜率法无法解释的实验事实。     

Extraction of Ce~(4+) from Tervalent Lanthanide with Immobilized Interface in a Microporous Hollow Fiber

中空纤维膜（ＭＨＦ）法研究了Ｃｅ４＋和三价稀土的溶剂萃取．结果表明Ｃｅ４＋的传质系数是Ｃｅ３＋和Ｌａ３＋的１０倍以上．Ｃｅ４＋的传质速度受水相临界层中扩散速度控制，ＲＥ３＋的传质速度受膜内扩散控制．Ｃｅ４＋能够从三价稀土中有效地分离．     

Synthesis of poly(hydroxymethylene-co-ethylene) by hydrogenation of the ethylene and carbon monoxide copolymer obtained by radical initiator with Ru/α-alumina and oxygen gas permeability

A new polymer (polyalcohol) was synthesized by hydrogenation of an ethylene carbon monoxide (CO) copolymer produced by a radical method with a catalyst and H₂. The Ru/α-alumina catalyst systems showed an excellent activity for hydrogenation of the radical copolymer of CH₂CH₂ and CO. Films prepared by melting and pressing the synthesized polyalcohol had a high gas barrier property and high tensile modulus. This new polymer has hydroxymethylenic units [ CH(OH) ] and ethylenic units [ CH₂CH₂ ] in its molecular structure. The new functional polymer poly(hydroxymethylene-co-ethylene),  [ CH(OH) ]_n[ CH₂CH₂ ]_m , is amorphous and has excellent and important properties as a high oxygen gas barrier film for wrapping and storage. This may be attributed to the new structure of poly(hydroxymethylene-co-ethylene) (PHME as an IUPAC name), or ethylene methine alcohol copolymer (EMOH as a generic name), compared to the other ethylene vinyl alcohol copolymer (EVOH as a generic name),  [ CH₂CH₂ ]_m [ CH₂CH(OH) ]_n , which is used as one of the highest gas barrier polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 889–900, 1998     

Acceleration of amine/epoxy reactions with N‐methyl secondary amines

Kinetic studies established that the monomethylation of a primary amine leads to significantly higher reaction rates with glycidyl ethers. The relative rates for approximately 25 amines were determined in an alcohol solvent under pseudo‐first‐order conditions (excess epoxy). The rates were referenced to aniline. For the aliphatic amines, reactivity consistently increased upon going from a primary amine to the corresponding N‐methyl secondary amine. This acceleration effect was not seen for aniline. The enhanced reactivity was also seen in curing systems, both with pure methylated amine curing agents and with complex mixtures obtained from the partial methylation of polyamines. Economically viable partially methylated amine curing agents were obtained by the reductive alkylation of commercial polyamines with formaldehyde and by the reaction of monomethylamine with 3‐(N‐methylamino)propionitrile in the presence of hydrogen and a hydrogenation catalyst. Although actual cure performance is based on a complex combination of several factors, the acceleration due to monomethylation could be a useful tool for enhancing amine/epoxy curing reactions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 921–930, 2000     

Asymmetric Direct Aldol Reactions Catalyzed by a Simple Chiral Primary Diamine–Br⊘nsted Acid Catalyst in/on Water

Abstract

The direct asymmetric aldol reaction catalyzed by the simple and commercially available chiral primary diamines, (1S,2S)-1,2-diphenylethane-1,2-diamine and (1R,2R)-1,2-diphenylethane-1,2-diamine, is presented. The catalyst system is a primary amine with Br?nsted acid–catalyzed direct aldol reaction of p-nitrobenzaldehyde and cyclohexanone with high chemo- and stereoselectivity on water, which furnishes the corresponding β-hydroxyketone with up to 94% ee.     

Base promoted peroxide systems for the efficient synthesis of nitroarenes and benzamides

A useful and efficient approach for the synthesis of nitroarenes from several aromatic amines (including heterocycles) using peroxide and base has been developed. This oxidative reaction is very easy to handle and afforded the products in good yields. Formation of benzamides from benzylamine was also successfully carried out with this metal-free catalytic system in good to excellent yields.     

Strong fluorescence emission from PEGylated hyperbranched poly(amido amine)

Hyperbranched poly(amido amine)s (HPAA) show weak photoluminescence, however, they have shown strong emission after short polyethylene glycol (PEG) chains have been linked onto HPAA macromolecule via Michael addition reaction. These PEGylated hyperbranched poly(amido amine)s show low cytotoxicity and potential application in cell imaging.