反应注射成型聚氨酯互穿聚合物网络研究——刚性网络对于体系形态及性能的影响

用微型反应注射成型机制备了以聚氨酯(PU)为弹性相的两类同步互穿聚合物网络(SIN),其刚性相分别采用保留仲羟基的乙烯基酯树脂(VERH)以及封闭仲羟基的乙烯基酯树脂(VERA)。用傅里叶变换红外光谱在线跟踪了这类互穿网络的生成过程,发现刚性网络抑制了PU网络中硬段有序结构的形成,两个网络间有一定程度的互穿,而两个网络间的化学键作用进一步削弱氢键强度。自旋—自旋弛豫时间的测定进一步表明网络间存在一定的互穿以及刚性相对于PU硬段结晶的抑制作用。材料的力学性能与其SIN的形态有关。VERA网络对PU表现出明显的增强作用,而由VERH网络形成的SIN则由于体系相分离进程受到严重阻碍而使材料性能恶化。     

The role of ester groups in resistance of plant cell wall polysaccharides to enzymatic hydrolysis

Xylan backbones in native plant cell walls are extensively acety-lated. Previously, no direct investigations as to their role in cellulolytic enzyme resistance have been done, though indirect results point to their importance. An in vitro deesterification of aspen wood and wheat straw has been completed using hydroxylamine solutions. Yields of 90% acetyl ester removal for both materials have been accomplished, with little disruption of other fractions (i.e., lignin). Apparently, as the xylan becomes increasingly deacetylated, it becomes 5–7 times more digestible. This renders the cellulose fraction more accessible, and 2–3 times more digestible. This effect levels off near an acetyl removal of 75%, where other resistances become limiting.     

离子液体两相不对称氢甲酰化催化反应的研究

从(R)-BINAP出发制备水溶性磺酸钠盐配体(R)-BINAPS,采用离子液体BF4和PF6为介质,实现其Rh配合物对乙酸乙烯酯的两相不对称氢甲酰化反应.实验结果表明,在以BF4为介质的乙酸乙烯酯不对称氢甲酰化反应中,该催化剂在温和条件下显示出高于相应均相体系的产物ee值和异构醛选择性,并在6次循环使用中,反应产物的ee值、选择性和转化率均无明显改变;在离子液体体系中添加适当的甲苯时,油溶性配体(R)-BINAP与Rh组成的配合物催化剂亦可形成类似的两相反应体系,但其活性和选择性在重复使用中呈明显下降趋势.本文还考察了溶剂体系、膦铑比、温度、压力、时间等的影响,并尝试苯乙烯的两相不对称氢甲酰化反应.     

Total synthesis of 1-(Z)-atractylodinol

The total synthesis of 1-(Z)-atractylodinol, a natural polyacetylenic alcohol with several biological activities, has been achieved using a newly developed telluride synthon and a novel use for the Negishi type coupling reaction employing vinyl tellurides.     

醋酸乙烯酯-马来酸酐共聚物与水解聚丙烯酰胺高分子络合物的研究

<正> 某些高分子在溶液中可以通过次价力形成高分子络合物.根据次价力的不同,可分为四类:聚电解质络合物、氢键络合物、立体络合物和电荷转移络合物.部分水解聚丙烯酰胺(简称HPAM)是在水悬浮体中被广泛使用的絮凝剂,醋酸乙烯酯-马来酸酐共聚物(简称VAMA)是一种能力很强的泥浆稀释剂.研究二者在水溶液中的相互作用,在理论上和应用上都有重要意义.我们曾研究了粘土对它们的吸附作用、改变泥浆流变性以     

Enthalpic determinations of aliphatic ester-solvent systems with correlations

Calorimetric measurements were carried out on ester-solvent systems where the esters were H(CH₂)_xCOO(CH₂)_yH, with x and y varying from 1 to 5, and the solvents were n-hexane and 1,2-dichloroethane. Calculation of the enthalpies of cavity formation enabled the enthalpies of interaction to be determined. Both enthalpies correlated with number of carbon atoms N, equal to x+y in the esters, giving for 1,2-dichloroethane

Synthesis of Nonracemic 9-(1-Methoxycarbonylethyl)-1,2,3,4-tetrahydrocarbazole

A new approach has been proposed to the synthesis of indole derivatives containing a chiral substituent at the nitrogen atom, comprizing Fischer indolization of phenylhydrazines with a chiral substituent at the -nitrogen atom. The initial hydrazines were obtained by the alkylation (Mitsunobu reaction applying optically active esters of lactic acid) of anilines containing an electron-accepting substituent at the amino group. Subsequent removal of the activating acceptor grouping was realized by nitrosation of the chiral secondary aniline followed by reduction of the corresponding N-nitroso compound.     

KINETIC MODELING OF ESTERIFICATION OF EPOXY RESIN IN THE PRESENCE OF TRIPHENYLPHOSPHINE FOR PRODUCING VINYL ESTER RESIN: MECHANISTIC RATE EQUATION

Due to its mechanical properties and ease of use, vinyl ester resin is enjoying increasing consideration. This resin normally is produced by reaction between epoxy resin and unsaturated carboxylic acid. In the present study, bis-phenol A based epoxy resin and methacrylic acid was used to produce vinyl ester resin. The reaction was conducted under both stoichiometric and non-stoichiometric conditions in the presence of triphenylphosphine as catalyst. The stoichiometric and non-stoichiometric experiments were conducted at 95, 100, 105 and 110℃and at 90 and 95℃, respectively. The first order rate equation and mechanism based rate equation were examined. Parameters are evaluated by least square method. A comparison of mechanism based rate equation and experimental data show an excellent agreement. Finally, Arrhenius equation and activation energy were presented.     

Stereoselective synthesis of (Z)-γ-cyano-β-perfluoroalkyl-β,γ-unsaturated esters

(Z)-γ-Cyano-β-perfluoroalkyl-β,γ-unsaturated esters have been synthesized by the reaction of perfluoroacylated phosphonates with organozinc reagent in 50-71% (three steps) yields.