Examination of Polymeric Azomethine Compounds and Their Transition Metal Complexes by Using XRF and XRD Technique

In this study,the electronic transition properties and structural analysis of the metal complexes(Ni(Ⅱ),Co(Ⅱ),Cu(Ⅱ)and Mn(Ⅱ))of three different polymer ligands were performed by using XRF and X-ray diffraction(XRD)techniques,respectively.The structural analysis of the polymers and their complexes were performed by XRD technique and some of the polymers were found to be in the face-centred cubic(fcc)structure.In addition,the values of the present K X-ray intensity ratios are significantly greater than the values reported in literature.

POLYMER SUPPORT EFFECTS OF METAL COMPLEXES FOR CATALYSIS

In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental results time and again indicate the presence of effects of macromolecular supports - the utilization of macromolecular supports increases obviously the activity, selectivity, and stability of the catalysts and so as to increase the conversion of substrates, yields of reactions, properties of formed polymers and so on. Discussed these effects on the basis of the authors' experiments. (Author abstract) 18 Refs.

Highly active double metal cyanide complexes: Effect of central metal and ligand on reaction of epoxide/CO2

Various novel double metal cyanide （DMC） catalysts were successfully prepared by modifying the central metal （M） and one of cyanide ion （CN-） in Zna[M（CN）b]c complex. Such modifications have significant impact on the catalytic efficiency as well as the polymer selectivity for the reaction of PO/CO2. Zn-Ni（Ⅱ） DMC is a potential catalyst for alternating copolymerization of PO/CO2,and DMC catalysts based on Zn3[Co（CN）5X]2 （X = Br^- and N3^-） exhibit moderate efficiency for the production of polycarbonates.This research presents the preliminary exploration of novel DMC complex via chemical modification of its central metal and ligand.

Preparation and Aqueous Recognition of Metal Complex Imprinted Polymer Using N-vinyl-2-pyrrolidone as Functional Monomer

Using nickel（II） acetate.-2,2＇-dipyridyl complex as template and N-vinyl-2-pyrrolidone （NVP） as coordinate functional monomer,.a new kind of metal-compiexing template molecularly impnnted polymer （MIP） was prepared..The results of equilibri.um binding experiments in. aqueous solution showed that the MIP had higher＇binding capacity for nickel（ II ）-2,2＇-dipyridyl than the non-imprinted polymer with the same chemical composition. Theinfluences of metal ions and pHof solution on the recognition performance of MIP were investigated. The bindingcharacteristics of MIP were evaluated by the Scatchard analysis with one-site and two-site binding equations, respectively. The results on substrate selectivity of imprinted polymer revealed that MIP had better binding affinityfor template among thetested compounds.

Antioxidant activity of bovine serum albumin binding amino acid Schiff-bases metal complexes

Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.

Calcium chloride doped zinc-cobalt metal-cyanide complex:Unexpected highly activity towards ring-opening polymerization of propylene oxide

Highly active calcium chloride（CaCl2） doped Zn-Co^Ⅲdouble metal-cyanide（Ca-DMC） catalysts were firstly reported.Ca-DMCs presented a very higher polymer yield（54 kg polymer/g catalyst） at relative low temperature（80-115℃） toward ringopening polymerization（ROP） of propylene oxide（PO） than did DMC catalysts without modification.

Studies on Polymeric Crown Ethers (Ⅰ)——The Syntheses and Complexation Properties of Polymeric Thiacrown Ethers with Polyether Backbone

Four new polymeric oxa-thiacrown ethers were prepared by the intramolecular cy-clization of poly (2-chloroethylglycidyl ether) with dimercaptans, which is the most convenient method for synthesizing poly(thiacrownether)s. The poly(thiacrownether)s exhibited excellent complexation properties for noble metal ions such as Au ( Ⅲ ) , Pd ( Ⅱ ) and Ag( Ⅰ ) , except Pt( Ⅳ ). In addition, the XPS of polymeric thiacrown ether (PC3) and its complexes of Au( Ⅲ ) and Pd( Ⅱ ) were determined.

PREPARATION OF FUNCTIONAL MATERIALS BY BLENDING COPOLYESTERS WITH PVA AND METAL COMPLEX FORMATION OF POLYMER BLENDS

Copolyesters having secondary and tertiary amine salt groups in the main and side chains are prepared by chemoselective polymerization. These copolyesters are soluble in a 10% aqueous solution of poly(vinyl alcohol) (PVA) at 90 degree C and act as plasticizer in the blend films cast from the solution. Only a glass transition temperature is observed for all these blends indicating the formation of compatible blends from these polyesters with PVA. These blends exhibit manifold characteristics such as ionic conductivity, complex formation with metal ions, absorption of moisture and color changes. The electric conductivity of the copolyesters and blends is in the range of 10** minus **6 Scm** minus **1. The blends with PVA forms complexes with Cu**2** plus and Co**2** plus . The coordination structure with two chelate rings is suggested for these polymer blend/metal complexes. (Author abstract) 10 Refs.

Synthesis of pyrrolidinyl-ethylene fluorenyl rare-earth metal complexes and catalysis for 2-vinylpyridine polymerization

The metathesis reaction between pyrrolidinyl-ethylene fluorenyl lithium salts with in situ prepared cationic rare-earth metal dialkyl species[Ln(CH_(2)SiMe_(3))_(2)(THF)_(x)][BPh_(4)]afford efficiently the corresponding constrained-geometry complexes L^(1)Ln(CH_(2)SiMe_(3))_(2)(L^(1)=FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(1a),Lu(1b),Sc(1c))and L^(2)Ln(CH_(2)SiMe_(3))_(2)(L^(2)=(2,7-di-tert-butyl)FluCH_(2)CH_(2)NC_(4)H_(8),Ln=Y(2a),Lu(2b),Sc(2c))in good yields.All these complexes were characterized by NMR spectroscopy,and the solid-state molecular structure of yttrium complex 1a was defined with single-crystal X-ray diffraction analysis.The catalytic performance of these complexes towards 2-vinylpyridine polymerization was investigated,where these complexes alone can efficiently promote the polymerization of 2-vinylpyridine giving isotactic poly(2-vinylpyridine).Upon the activation with[Ph_(3)C][B(C_(6)F_(5))_(4)],the yttrium and lutetium complexes also afford isotactic poly(2-vinylpyridine),while the scandium complexes produce syndiotactic poly(2-vinylpyridine).

Preparation Physicochemical Characterization and Catalytic Applications of Polystyrene Ethylenediamine Tetra acetic Acid Cu(II) Metal Complex

Chloromethylated styrene-divinylbenzene copolymer beads with 8% crosslink were chemically modified by reaction with Ethylenediaminetetraaceticacid leading to the incorporation of nitrogen as ligating site on the surface of the polymer. The polymeric ligand on treatment with a solution of Copper chloride gave the corresponding metal complex. The polymer supported Cu(II) complex was characterized by elemental analyses, IR,GC-MS, scanning electron micrographs (SEM). The oxidation of various alcohols such as benzyl alcohol, 2-butanol, and 2-propanol was investigated using the supported metal complexes in presence of molecular oxygen as the oxidant. The swelling studies were done by using different solvents. Kinetic data indicate that the catalysts could be recycled without significant degradation of polymer matrix.

吲哚基NCN钳型钛族金属配合物的合成及其催化苯乙烯聚合反应

以吲哚为骨架,在吲哚的1位、3位引入2条边臂基团得到了1,3-双取代吲哚基化合物,用丁基锂去质子后与MCl_(4)(M=Ti、Zr、Hf)反应,得到一系列NCN钳型钛、锆、铪金属配合物(3-Ti、3-Zr、3-Hf)。该系列配合物通过核磁、元素分析及单晶X射线衍射进行了表征。单晶结构显示,金属中心除与3个氯原子配位外,还与配体以κ^(3)_(NCN)的形式配位,形成六配位的八面体构型。考察了该类型配合物在不同助催化体系条件下催化苯乙烯聚合反应的性能。实验发现:在室温下,助催化剂为AlEt_(2)Cl/(Ph_(3)C)[B(C_(6)F_(5))_(4)],甲苯为溶剂,单体与催化剂在浓度比300∶1的条件下,不同金属中心配合物都能以高转化率得到聚苯乙烯,其中铪配合物的催化活性最高。催化所得的聚苯乙烯经表征发现均为无规结构,数均分子量为4 000~8 000。

蒽基取代含酚单茂催化剂在乙烯聚合中的应用

以蒽基取代的含酚单茂催化剂为主催化剂,三苯甲基四(五氟苯基)硼酸盐为助催化剂进行了乙烯均聚和乙烯/α-烯烃共聚反应,利用DSC,GPC等方法考察了该催化体系在不同聚合条件下的聚合性能。实验结果表明,该催化体系催化乙烯均聚的活性最高可达到3.36×10^(6)g/(mol·h)。适宜的聚合条件为:催化剂用量10μmol,n(Al)∶n(Ti)=150,n(B)∶n(Ti)=1.5,反应温度20℃,反应压力0.4 MPa,聚合时间10 min,液体总体积200 mL。在该条件下还可催化乙烯与α-烯烃共聚,其中,与1-辛烯共聚时,聚合活性最高可达2.00×10^(6)g/(mol·h),共聚物密度在0.859~0.876 g/cm3之间,玻璃化转变温度均低于-52℃,符合乙烯共聚弹性体的结构性能特征,且通过调节共聚单体浓度能有效控制乙烯共聚物链结构。

过渡金属配合物催化烯烃配位聚合综合实验的设计——催化剂构效关系的典型案例

文章介绍了一个涉及合成化学多领域的综合实验,要求学生利用合成的有机配体制备相应的过渡金属配合物,并作为催化剂均相催化烯烃配位聚合,同时对所得聚合物性能进行测试。该实验串联了有机配体合成、金属配合物合成、高分子催化合成和高分子材料性能测试模块的内容,能让学生观察到烯烃配位聚合中的催化剂构效关系,有利于全面提高学生的学习兴趣、实验技能和独立思考能力。

富含间规聚苯乙烯链段的乙烯/苯乙烯共聚物的合成及力学性能

文中采用半夹芯型稀土金属配合物催化乙烯和苯乙烯共聚,合成了一系列具有不同共聚单体组成、富含间规聚苯乙烯链段的乙烯/苯乙烯共聚物。通过控制苯乙烯的投入量调控共聚物中乙烯的插入率,研究了乙烯插入率对共聚物熔点和力学性能的影响。结果表明,当乙烯插入率从9.6%升高到27.6%,共聚物中间规苯乙烯连续链段变短,熔点从256.3℃逐渐降低至241.4℃;当乙烯摩尔分数为72.9%时,表现出类似乙烯的熔点126.3℃。随着乙烯插入率的升高,材料的拉伸强度、弯曲强度逐渐降低,断裂伸长率、冲击强度逐渐升高,将乙烯插入间规聚苯乙烯链段有效改善了材料的脆性。当共聚物中乙烯摩尔分数为22.0%时,拉伸强度和冲击强度分别为54.3 MPa和20.4 kJ/m^(2)。文中合成的乙烯/苯乙烯共聚物强度大、熔点高,并具有一定的韧性。

双金属氰化物催化剂的制备、表征及其催化性能

以丙烯酸-异戊烯醇聚氧乙烯醚梳型共聚物为分散剂,通过分散聚合制备了高活性的双金属氰化物催化剂。元素分析和红外光谱证实了分散剂不仅起分散稳定作用,也参与了催化剂化学结构的形成。X射线衍射谱图和热失重分析说明分散剂与中心金属离子发生了直接络合作用,晶型发生畸变,趋向于无定形态。扫描电镜进一步表明分散法制备的催化剂整体尺寸明显小于直接沉淀法,形貌由紧密的片层状结构转变成更松散的无序堆积。得益于催化剂比表面积增加和单位面积上活性位点的增多,分散法制备的双金属氰化物的催化活性高达66585 g/g催化剂,远高于直接沉淀法(8245 g/g催化剂)。循环实验显示分散法制备的催化剂具有较好的循环能力,在第五次循环时催化活性仍能达56997 g/g催化剂(85.6%),远高于直接沉淀法的1501 g/g催化剂(18.2%)。

Synthesis and characterization of aminophenolate-ligated rare-earth metal amide complexes and their catalytic activity for lactides polymerization

Amine elimination of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with aminophenol H[ON]{H[ON]=2-(CH2 NC5 H10)-4,6-tBu2-C6 H3OH}in 1:2 molar ratio in THF gave the monometallic rare-earth metal amide complexes[ON]2 LnN(SiMe3)2(Ln=Yb(1),Y(2),Gd(3),Sm(4),Nd(5))in 57%-73%isolated yields.All these complexes were characterized by elemental analysis.The molecular structures of complexes 1-4 were determined by single crystal X-ray diffraction.These complexes are highly active for L-Iactide polymerization to give high molecular weight polymers with unimodal molecular weight distributions.In addition,these complexes can also initiate rac-lactide polymerization with high activity to afford heterotactic-rich polylactides.

SYNTHESES,CHARACTERIZATION AND ETHYLENE POLYMERIZATION OF HALF-SANDWICH GROUP IV METAL COMPLEXES WITH TRIDENTATE [O,N,S] LIGANDS

A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.

Rare-earth Metal Dialkyl Complexes Supported by 1,3-Disubstituted Indolyl Ligand: Synthesis, Characterization and Catalytic Activity for Isoprene Polymerization

Rare-earth metal dialkyl complexes[1-Bn-3-(DippN=CH)C_(8)H_(4)N]RE(CH_(2)SiMe_(3))2(thf)2(Dipp=2,6-iPr_(2)C_(6)H_(3),RE=Y(1)and Er(2))were prepared through the cyclometalation reactions of the N-Bn-3-imino-functionalized indolyl ligand 1-Bn-3-(DippN=CH)C8H5N with one equivalent of rare-earth metal trialkyl precursors.The structures of compounds 1 and 2 were confirmed by X-ray crystal analyses and characterized by elemental analysis,IR,NMR spectroscopy wherein applicable.In the presence of cocatalysts,these rare-earth metal dialkyl complexes initiated isoprene polymerization with a high activity(95% conversion of 2000 equivalent of isoprene in 360 min),producing polymers with high regioselectivity(1,4-polymers up to 91%).

Recent progress in immobilization of late-transition-metal complexes with diimine ligands for olefin polymerization

Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand structure.Their less oxyphilicity character,which may promote the production of copolymers from ethylene and polar comonomers,is another aspect that attracts much attention in both academic and industrial fields.The immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry polymerizations.This paper reviews recent developments in supported LTM catalysts for olefin polymerization,and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic,organic,and inorganic-organic materials,and the effects of immobilization on catalytic activity,polymerization mechanism,and polymer morphology.

Transition metal complexes bearing 2,6-bis(imino)pyridyl:Synthesis, structure, ethylene polymerization/oligomerization studies

A series of new complexes {2,6-bis[1-((2-methyl-4-methoxyphenyl)imino)ethyl]pyri-dine}MCI2 [M=Fe(Ⅱ) (2), Co(Ⅱ) (3), Ni(Ⅱ) (4), Cu(Ⅱ) (5), Zn(Ⅱ) (6)] have been synthesized. At 25℃, using 500 equiv of methylaluminoxane (MAO), the activities of Fe(Ⅱ), Co(Ⅱ) catalysts can reach 4.02×106 g/mol-Fehatm for ethylene polymerization and 3.98×105 g/mol-Cohatm for ethylene oligomerization. The effects of polymerization conditions such as reaction temperature, Al/M molar ratio and time on the activity of catalyst have been explored.