Low-pressure pyrolysis studies of a new phosphorus precursor: Tertiarybutylbis(dimethylamino)phosphine

The low pressure decomposition of tertiarybutylbis(dimethylamino) phosphine, (t-Bu)P(NMe₂)₂, (TBBDMAP), has been studied on quartz and deposited GaP and InP surfaces. This new phosphorus precursor has been found to pyrolyze on quartz surfaces at much lower temperatures than the related compounds tertiarybutylphosphine, (t-Bu)PH₂, (TBP) and tris(dimethylamino)phosphorus, P(NMe₂)₃, (TDMAP). In contrast to the results obtained for TDMAP, GaP and InP surfaces decrease the decomposition temperature of TBBDMAP only slightly. The TBBDMAP reaction products were dimethylamine, methylmethyleneimine, and isobutylene, consistent with previous pyrolysis studies of TBP and TDMAP.     

Synthesis and characterization of new flame‐retardant poly(amide‐imide)s containing phosphine oxide and hydantoin moieties in the main chain

Six new flame‐retardant poly(amide‐imide)s (PAIs) 9a–f with high inherent viscosities containing phosphine oxide and hydantoin moieties in main chain were synthesized from the polycondensation reaction of N,N′‐(3,3′‐diphenylphenylphosphine oxide) bistrimellitimide diacid chloride 7 with six hydantoin derivatives 8a–f by two different methods such as solution and microwave assisted polycondensation. Results showed that the microwave assisted polycondensation, by using a domestic microwave oven, proceeded rapidly, compared with solution polycondensation, and was completed in about 7–9 min. All of the obtained polymers were fully characterized by means of elemental analysis, viscosity measurements, solubility test, and FTIR spectroscopy. Thermal properties and flame retardant behavior of the PAIs 9a–f were investigated using thermal gravimetric analysis (TGA and DTG) and limited Oxygen index (LOI). Data obtained by thermal analysis (TGA and DTG) revealed that these polymers showed good thermal stability. Furthermore, high char yields in TGA and good LOI values indicated that these polymers are capable of exhibiting good flame retardant properties. These polymers can be potentially utilized in flame retardant thermoplastic materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5062–5071, 2006     

Catalytic hydrogenation of nitrile rubber using palladium and ruthenium complexes

The catalytic hydrogenation of acrylonitrile‐butadiene copolymer (nitrile rubber, NBR) using Pd(OAc)₂ or RuCl₂(PPh₃)₃ catalysts has been investigated in order to produce a totally saturated nitrile rubber. The hydrogenation of NBR is effective with both catalysts and achieved total conversion under the appropriate reaction conditions. In the case of palladium the effects of reaction parameters such as reaction temperature, pressure, time, catalyst concentration, and NBR concentration have been investigated. Even though both ruthenium‐ and palladium‐based catalysts are effective in the production of HNBR, the former requires harsh reaction conditions and has the drawback of gel formation under high conversion, motivating the migration to RuCl₂ (PPh₃)₃ as an alternative catalyst. The degree of hydrogenation was determined by IR and NMR spectroscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

三烷基氧膦络合萃取一元有机羧酸

络合萃取法对极性有机物稀溶液的分离具有高效性和高选择性。选择甲酸、乙酸、丙酸、丁酸为分离对象 ,三烷基氧膦 (TRPO)为络合剂 ,煤油为稀释剂 ,进行了系统的萃取相平衡实验 ,测定了络合剂浓度、稀释剂组成等因素对萃取平衡分配系数的影响。实验结果表明 ,溶质的亲油性对络合萃取平衡影响起主导作用 ;随TRPO浓度增大 ,萃取平衡分配系数呈增大趋势 ;随溶质初始浓度增大 ,有机相的溶质浓度向饱和萃取量接近 ;饱和萃取量随络合剂浓度的增大而增大。对相平衡分配系数进行拟合 ,精度令人满意。     

二氧化硅负载支链有机膦的合成及其在二氧化碳催化氢化反应中的催化性能

以改性二氧化硅为核,利用发散法合成出二氧化硅负载的1～6代端胺基树枝状高分子(SiO2-PAMAM),样品经FT-IR,TG和端胺基分析表征.利用功能化载体表面的氨基与[Ph2P(CH2OH)2]+Cl-发生反应,合成出SiO2-PAMAM负载的有机膦(SiO2-PAMAM-PPh2),与三氯化钌复配成催化体系,考察了其对吗啉存在下的二氧化碳催化氢化反应的催化性能,该催化体系的催化活性(TOF)可达4 195.     

氢氧化铝/膦掺杂丙烯酸树脂的热稳定性和协同阻燃效应

采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与甲基丙烯酸-β-羟乙酯反应得到膦化物2-甲基-3-(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)丙酸2-羟乙酯(DOPO-HM),将氢氧化铝(Alu)与DOPO-HM掺杂到丙烯酸树脂(AR)制备丙烯酸树脂阻燃复合材料AR/DOPO-HM/Alu。通过热重分析、极限氧指数(LOI)、扫描电镜、X射线光电子能谱(XPS)对复合材料及炭层进行分析。研究表明,DOPO-HM/Alu体系能协同提高复合材料的热稳定性和LOI,复合材料在空气和氮气中热分解炭层致密。XPS研究阻燃机理揭示DOPO-HM的分解产物聚磷酸催化分解基体成炭过程在Al2O3表面进行,焦磷酸铝的生成证明存在协同阻燃效应。Horowitz-Metzger理论计算复合材料的分解活化能,结果表明Al2O3对膦催化复合材料分解成炭过程具有正向助催化作用,协同提高复合材料阻燃效力。     

季鏻盐杀菌剂的合成新方法与杀菌特性研究

研究了季鏻盐合成的新方法,包括格氏试剂、三丁基膦和鏻盐的合成方法。该方法的特点是可将溶剂回收再利用,提高了溶剂的使用效率;并且采用新的控制步骤使产品收率达70%,可实现工业化生产。     

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.     

化学需氧量和总磷对猪场废水产磷化氢的影响

以猪场原液和沼液作为研究对象,在遮光密闭的环境中,于厌氧序批式反应器(ASBR)内利用钼酸铵分光光度法分别测定单位时间内不同COD和TP浓度下PH3的产生量。结果表明:猪场原液和沼液PH3释放量分别达0.048、0.033 mg/h;COD和TP都能促进磷化氢的产生。     

The Lithiation Reactivity and Selectivity of Differentially Branched Alkyldiphenylphosphine Oxides – A Simple and Versatile Approach to ortho‐Functionalized Arylphosphine Oxides

Alkyldiphenylphosphine oxides typically undergo α‐deprotonation with alkyllithium reagents. Here, the lithiation of differentially branched alkyldiphenylphosphine oxides was investigated and a diverse, but predictable reactivity was found. γ‐Branched derivatives undergo selective directed ortho‐metalation (DoM) using butyllithium and TMEDA as an additive. With decreasing degree of γ‐branching α‐lithiation becomes predominant. The ortho‐phosphinoyllithium intermediates are subject to functionalization and C C bond forming reactions, thus providing a convenient approach to new phosphine oxides and phosphine‐borane complexes, which have a good potential for an approach to new ligands for catalysis.