两个Pd(II)的异亚硝基乙酰丙酮亚胺配合物的合成和表征

合成了两个异亚硝基乙酰丙酮亚胺Pd(II)配合物，Pd(o-BrC_6H_4-IAI)_2 (1) 和Pd(C_6H_5CH_2-IAI)_2 (2)（IAI = isonitrosoacetylacetoneimino），用IR和 Raman光谱对两个配合物进行了表征，并测定了配合物1的晶体结构。配合物1晶体 属单斜晶系，空间群为P2_1/c，晶胞参数：a = 0.8013(2) nm，b = 1.8775(4) nm，c = 0.7905(2) nm，β = 98.22(3)°，V = 1.1770(5) nm~3，Z = 2，D_c = 1.892 g·cm~(-3)，F(000) = 656，R = 0.0663。在这两个配合物中，二齿 Schiff碱配体的异亚硝基（肟基）的N原子和亚胺的N原子与Pd(II)配位，形成反式 的PdN_4平面正方形配位构型。     

δ-（甲酰乙烯基）二氢卟吩衍生物的合成

以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.     

交联聚乙烯基吡咯烷酮的合成及其性能研究

以乙烯基吡咯烷酮（NVP）为单体，二乙烯基苯为交联剂，AIBN为引发剂，采用悬浮聚合法合成了性能稳定的交联聚乙烯基吡咯烷酮（PVPP），研究了聚合温度，引发剂用量，交联剂用量和反应气氛等因素对产率，溶胀性能和吸附性能的影响，并用红外光谱和扫描电镜等对产物的结构、性能和表面形貌进行了表征。     

IMPROVED PROPERTIES OF METALLOCENE-CATALYZED LINEAR LOW-DENSITY POLYETHYLENE/POLYPROPYLENE BLENDS DURING ULTRASONIC EXTRUSION

Metallocene-catalyzed linear low-density polyethylene/polypropylene （mLLDPE/PP） blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by online measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends.     

烯烃的有机催化不对称环氧化反应

介绍了用手性酮，手性亚胺盐为催化剂以及手性胺为催化剂前体的新型有机催化不对称环氧化反应。     

PREPARATION OF POLY（METHYL METHACRYLATE）/LAYERED DOUBLE HYDROXIDES NANOCOMPOSITES via in situ SOLUTION POLYMERIZATION

An exfoliated layered double hydroxides/poly(methyl methacrylate)(LDHs/PMMA)nanocomposite was prepared by in situ solution polymerization of methyl methacrylate(MMA)in the presence of 4-vinylbenzenesulfonate intercalated LDHs(MgAl-VBS LDHs).MgAl-VBS LDHs was prepared by the ion exchange method,and the structure and composition of the MgA1-VBS LDHs were determined by X-ray diffraction(XRD),infrared spectroscopy and elemental analysis.XRD and transmission electron microscopy(TEM)were employed to examine the structure of LDHs/PMMA nanocomposite.It was indicated that the LDHs layers were well exfoliated and dispersed in the PMMA matrix.The grafting of PMMA onto LDHs was confirmed by the extraction result and the weight fraction of grafted PMMA increased as the weight fraction of LDHs in the nanocomposites increased.     

高分子钯络合物催化的亚胺化合物的加氢反应

制备了一系列以二氧化硅为载体的侧链上含有各种氮配位基团的聚硅氧烷-钯络合物,这些高分子钯络合物能够在常温常压下催化亚胺化合物的加氢反应并表现出不同程度的催化活性.对其中聚-(N,N-二乙酰基)-γ-氨丙基硅氧烷-钯络合物催化的亚苄基苯胺的加氢反应做了比较深入的研究,发现该催化剂在反应中是稳定的并给出唯一的加氢产物,络合物中的N/Pd原子比、反应温度以及不同底物对反应速度的影响也被报道.     

SYNERGISTIC MODIFICATION OF EPDM AND CROSSLINKING AGENT IN IMMISCIBLE BLENDS OF POLYVINYL CHLORIDE WITH LOW DENSITY POLYETHYLENE

The synergism of ethylene-propylene-diene monomer copolymer （EPDM） and dicumyl peroxide （DCP, a crosslinking agent） in low density polyethylene （LDPE）/poly（vinyl chloride） （PVC） blends was investigated. When EDPM and DCP are added to the blends simultaneously, the tensile properties could be improved significantly, especially for the blends with LDPE matrix. For example, incorporation of 10/1 （mass ratio） EPDM/DCP improves the tensile strength of the LDPE/PVC （mass ratio 80/20） blend from 7.9 MPa to 8.5 MPa and the elongation at break from 25% to 503%. Results from selective extraction, phase-contrast microscopy and thermal analysis reveal that the improvement in the tensile properties of the blends with LDPE matrix is principally due to the formation of a fine crosslinking network of the LDPE and EPDM phase. The outstanding modification effect of EPDM is explained by its dual functions： molecular entanglement with LDPE and the enhanced efficiency of DCP in the blends.     

官能化蒙脱土负载双金属催化芳香氯化物水相脱氯

用PVP(聚乙烯吡咯烷酮)络合双金属Pd^2 ,Sn^4 后，再负载于用PEG400(平均分子量为400的聚乙二醇)官能化的蒙脱土上，制成双金属催化剂PVP—PdCl2-SnCl4/Montk10-PEG400,用于催化难溶于水的芳香卤化物水相脱卤，芳香族氮化物转化率达100％，该催化剂可重复使用。对催化剂进行了IR及TEM表征。     

固相氯化法合成氯化聚乙烯的红外光谱研究

本文研究在不同条件固相氯化聚乙烯(CPE)的红外光谱,探讨了一步和两步氯化合成的CPE的结构差别,着重讨论了两步氯化的CPE结构特点。从观察表征结晶结构和—(CH_2)_n—链段氯分布的特征频率变化表明,低温固相氯化主要发生在无定形区,并且在CPE中形成高氯化和低氯化链段(或未氯化)的嵌段结构。在两步固相氯化时,晶区受到较大程度的破坏,氯化作用已不局限在无定形区,其结晶结构的破坏主要同第二步氯化程度有关,即使CPE氯含量相同,若前后两步氯化程度不同,结构有很大差异。