三苯基膦合成工艺改进

采用弗 克法 ,以苯 ,三氯化磷 ,硫磺直接回流反应 ,生成三苯基硫膦 ,再经锌粉还原制得三苯基膦。其中采用不分离出三苯基硫膦以及用锌粉作还原剂等新工艺。该法具有收率高 ,产品纯 ,反应条件缓和等特点。     

Kinetics of esterification of cycloaliphatic epoxies with methacrylic acid

The esterification of cycloaliphatic epoxy resins CER I and CER II containing glycidyl and cyclohexane epoxy groups, respectively, as their reactive units was carried out using a 1 : 0.9 stoichiometric ratio of resin and methacrylic acid in the presence of triphenylphosphine. The reaction was performed at 80, 85, 90, 95, and 100°C and it followed second‐order kinetics. The specific rate constants, calculated by regression analysis, were found to obey an Arrhenius expression. Kinetic and thermodynamic parameters, activation energy, frequency factor, entropy, enthalpy, and free energy of the reaction, revealed that the reaction was spontaneous and irreversible and produced a highly ordered activated complex. The reactivity of CER II was found to be higher than that of CER I. The difference in the reactivity of the cycloaliphatic epoxies was explained by proposing a reaction mechanism. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3197–3204, 2002     

三苯基膦及其衍生物的合成及应用

评述了三苯基膦和三苯基膦衍生物的合成及其应用的研究和发展概况。三苯基膦及其衍生物在有机合成中起着重要作用,主要是用于有机磷阻燃剂的中间体和两相水溶性催化剂中的配体。     

Lewis Base Additives Improve the Zeolite Ferrierite‐Catalyzed Synthesis of Isostearic Acids

Isostearic acids (IA) are highly utilized for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for efficient IA production through isomerization of fatty acids. The process utilized zeolite protonated Ferrierite with a small amount of base additive to neutralize (i.e., poison) the acidic sites on the external surfaces of the zeolite particles to prevent side reactions. Of the six base additives examined, the proton sponge combined with the zeolite protonated Ferrierite was found to be the most effective for this isomerization. With only 0.5 wt% proton sponge additive to 5.0 wt% Ferrierite, the dimers were successfully suppressed from 20.6 wt% yield to 2.42 wt% with an IA yield of 83.4 wt% and a 98 % conversion.     

ICP-AES法测定三苯基膦氯化铑中的微量杂质

将三苯基膦氯化铑用硝酸、高氯酸消解,以混合酸溶解样品,用ICP-AES法测定三苯基膦氯化铑中的微量Al、Cu、Fe、Mg、Pd、Ni、Pb、Pt、Zn杂质元素含量。选择合适波长消除光谱干扰,用背景点扣除的方式消除铑对Fe、Ni、Pb、Pt、Zn的基体干扰。各杂质元素的检测范围为0.001%~0.1%,加标回收率为93.25%~117.0%,精密度(RSD)为0.18%~15.41%。与直流电弧发射光谱分析方法相比,准确度和精密度均得到提高,高纯铑基体消耗减少,操作简化。     

Multifunctional Deep‐Blue Emitter Comprising an Anthracene Core and Terminal Triphenylphosphine Oxide Groups

A highly efficient blue‐light emitter, 2‐tert‐butyl‐9,10‐bis[4′‐(diphenyl‐phosphoryl)phenyl]anthracene (POAn) is synthesized, and comprises electron‐deficient triphenylphosphine oxide side groups appended to the 9‐ and 10‐positions of a 2‐tert‐butylanthracene core. This sophisticated anthracene compound possesses a non‐coplanar configuration that results in a decreased tendency to crystallize and weaker intermolecular interactions in the solid state, leading to its pronounced morphological stability and high quantum efficiency. In addition to serving as an electron‐transporting blue‐light‐emitting material, POAn also facilitates electron injection from the Al cathode to itself. Consequently, simple double‐layer devices incorporating POAn as the emitting, electron‐transporting, and ‐injecting material produce bright deep‐blue lights having Commission Internationale de L'Eclairage coordinates of (0.15,0.07). The peak electroluminescence performance was 4.3% (2.9 cd A^?1). For a device lacking an electron‐transport layer or alkali fluoride, this device displays the best performance of any such the deep‐blue organic light‐emitting diodes reported to date.     

Sodium storage properties of thin phosphorus-doped graphene layers developed on the surface of nanodiamonds under hot pressing conditions

Abstract

Phosphorus-doped graphene layers have been formed on the surface of nanodiamond (ND) particles by hot pressing of a mixture of purified detonation ND powder and triphenylphosphine (TPP) at 1000?°C and 100?bar. X-ray photoelectron spectroscopy detected about 1.7 at.% of phosphorus in the product, most of which was in the oxidized form. The same treatment conditions of the ND powder without the addition of TPP resulted in the only partial covering of some ND particles by sp²-hybridized carbon layers. The tests in Na-ion half-cells found that the pure carbon sample can reversibly sustain 42 mAh g^?1 at a current density of 0.1?A g^?1. For the phosphorus-doped sample, this value increases up to 54 mAh g^?1 due to mainly accumulation of sodium at various defects created in the graphitic layers as a result of phosphorus incorporation. Taking into account inertness of inner diamond cores, specific capacity values are 417 mAh g^?1 for phosphorus-doped graphene layers and 587 mAh g^?1 for non-doped ones.     

Two-component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates: The in situ cleavage of disulfides by triarlyphosphines

A two-component initiator system based on the in situ cleavage of phenyl disulfide by a triarylphosphine has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers. This development has potential use in composite applications such that the prepolymer can suitably wet the composite material before being converted to high-molecular-weight polymer. The initiator precursors (phenyl disulfide and triphenylphosphine) do not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. A mixture of cyclic BPA carbonate oligomers and one of the initiator components (phenyl disulfide), combined and heated at 300°C with a mixture of the cyclics and the other initiator component (triphenylphosphine), does produce a high-molecular-weight polymer (M_w = ∼ 70,000). The polymerization-initiating species is thought to be thiophenyltriphenylphosphonium thiophenoxide. The effects of concentration of the initiator components, reaction temperature, time, and so forth on polymerization were studied; in general, the degree of polymerization ranged from about 65 to 75%. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2251–2255, 1997     

苯酚催化氢转移制环己酮的新工艺

以3-(三苯基膦)二氯化钌[RuCl2(PPh3)3]作催化剂,甲酸钠为氢供体,研究了氢转移催化苯酚加氢制环己酮的新工艺。确定了氢转移加氢过程的适宜反应条件为：甲酸钠和苯酚用量摩尔比为4∶1,反应温度为70 ℃,反应时间为3.0 h,RuCl2(PPh3)3和苯酚用量质量比为5∶100。苯酚的转化率为100%,环己酮产率为95.1%。探讨了以甲酸钠为氢供体的反应过程,发现RuCl2(PPh3)3对苯酚氢转移加氢制环己酮具有优异的催化活性。     

二缩三丙二醇的合成工艺研究

以环氧丙烷和1,2-丙二醇为原料,用三苯基膦等作催化剂合成二缩三丙二醇,同时副产一缩二丙二醇,对其合成及精馏工艺条件进行了初步研究。通过正交实验得出最佳合成工艺条件。该工艺反应平稳,可控性好,二缩三丙二醇含量高,可以达到45%～55%,并讨论了对合成底物精馏提纯的最佳工艺条件。