氯化钕丙酰胺配合物催化4-乙烯吡啶聚合反应的研究

对氯化钕丙酰胺配合物与烷基铝组成的二元体系催化 4 乙烯吡啶极性单体聚合反应进行了研究 ,考察影响聚合反应的各种因素。氯化钕配合物催化活性随Al Nd(摩尔比 )、催化剂浓度、聚合时间的增加而增大 ,添加吡啶给电子体可提高氯化钕配合物催化活性。不同种类烷基铝对催化活性的影响活性顺序为 :(i Bu) 3Al>(i Bu) 2 AlH >Et3Al。聚合温度在 50℃时 ,配合物催化活性最高。     

聚合负载三氯化钕配合物的合成及其催化活性——含硫醇和亚砜基团的配合物

合成了含—CH     

吡啶-三唑金属配合物的合成及其在乙烯聚合反应中的催化性能

以苄氯、吡啶炔和叠氮化钠为原料,在铜(Ⅰ)催化下,通过Click反应制得新型配体1-苄基-4-邻吡啶基-1,2,3-三唑(1); 1分别与无水FeCl₂, CoCl₂或NiBr₂ ·DME反应合成了3个新型的吡啶基三唑金属配合物(2~4),其结构经¹H NMR, ¹³C NMR, IR和元素分析表征。考察了2~4对乙烯聚合反应的催化性能。结果表明：以甲基铝氧烷(MAO)为助催化剂, 4具有最高的催化活性,在温度为20 ℃, Al/Ni为2 500条件下,催化活性达8.8×10⁵ g·mol^-1·h^-1。     

聚合物载体-稀土金属配合物的研究ⅩⅠⅤ.聚(苯乙烯-丙烯酰胺)载体-氯化钕配合物对丁二

研究了聚（苯乙烯－丙烯酰胺）（ＰＳＡＣ）载体－氯化钕配合物催化丁二烯聚合的规律，考察了ＰＳＡＣ载体及ＰＳＡＣ．ＮｄＣｌ３配合物的组成与催化活性间的关系，ＰＳＡＣ载体的收率不影响配合物的活性，而配合物的活性却随ＰＳＡＣ载体中Ｃ（Ｏ）ＮＨ２功能团含量的高低而改变，含量低时活性高，ＰＳＡＣ载体与配合物的组成不影响所得聚丁二烯的微观结构。     

二（叔丁基环戊二烯基）钕甲基配合物催化丙烯腈聚合

二（叔丁基环戊二烯基）钕甲基配合物催化丙烯腈聚合任劲松，扈晶余，沈琪（中国科学院长春应用化学研究所稀土化学与物理开放实验室长春１３００２２）（苏州大学化学系苏州）关键词丙烯腈，配位聚合，钕配合物丙烯腈聚合通常采用ＢＦ＿３、ＴｉＣｌ＿４、过氧化苯甲酰￣...     

聚(苯乙烯-4-乙烯基吡啶)钕配合物的研究

含氮聚合物是一类很有意义的配位体,它在某些反应的催化过程中起载体作用。在含氮聚合物中,聚(苯乙烯-4-乙烯基吡啶)(PS4VPY)也是一种很重要的配体,因其杂环氮原子有一定的反应能力和配位能力。聚(4VPY)过渡金属(如Co、Ni、Cu和Zn)配合物已有报道。但PS4VPY的稀土配合物未见报道。本文报道NdCl_3·PS4VPY的合成和表征,及催化活性。     

氯化钕与二甲亚砜配合物的晶体结构

[Nd(DMSO)_5(H_2O)_3]Cl_3·H_2O的单晶用ENRAF-NONIUS CAD 4型四圆衍射仪收集衍射数据进行结构分析,最终偏离因子R=0.036。晶体属三斜晶系空间群P_1,晶胞参数a=9.800(1),b=10.531(1),c=14.757(2);α=93.07(1),β=100.2l(1),γ=99.71(1)°;Z=2。结构分析证实:晶胞中有二个[Nd(DMSO)_5(H_2O)_3]Cl_3·H_2O分子。Nd与五个DMSO及三个H_2O中的氧形成八配位的畸变三角十二面体结构。Cl~-与络阳离子通过离子键相互作用。[Tb(DMSO)_5(H_2O)_3)Cl_3·H_2O的晶胞参数与之相近,有类似的结构。     

聚合物载体-稀土金属配合物的研究ⅩⅦ聚(苯乙烯-4-乙烯基吡啶)钕配合物在丁二烯聚合中的催化行为

聚合物载体－稀土金属配合物的研究．聚（苯乙烯－４－乙烯基吡啶）钕配合物在丁二烯聚合中的催化行为李晓莉于广谦＊李玉良（中国科学院长春应用化学研究所长春１３００２２）关键词苯乙烯，乙烯基吡啶，共聚物，钕配合物，丁二烯聚合１９９６－０４－１１收稿，１９９６...     

二（2,6—二叔丁基—4—甲基苯氧基）钐配合物催化丙烯腈聚合

首次报道用稀土有机配合物作为单组份催化剂催化丙烯腈聚合，研究了聚合条件对标题化合物的催化活性和所得聚丙烯腈的分子量及其结构的影响。     

Neodymium Ziegler-Natta catalysts: Evaluation of catalyst ageing effect on 1,3-butadiene polymerization

Catalysts constituted by neodymium versatate, diisobutylaluminium hydride and t-butyl chloride were used in this work. After their synthesis, they were aged at 40 °C for 48 h. Afterwards, they were maintained at 10 °C for more 5, 15, 40, 80, 160 and 250 days and finally the aged catalysts were evaluated in butadiene polymerization. The polybutadienes were characterized by size exclusion chromatography (SEC) to determine the molecular weight characteristics and by infrared spectroscopy (FTIR) to determine the microstructure. The aim of this work is to evaluate the effect of ageing time on 1,4 polymerization of butadiene. The results showed that the stereoselectivity of the active sites was not affected by the ageing conditions. However, the catalyst activity increased for long times of ageing.     

Catalytic Activity of Polymer-Supported Neodymium Complexes in the Polymerization of Butadiene

The IR spectra of neodymium complexes supported on styrene-acrylic acid copolymer were investigated. The complexes possess a bidentate carboxylate structure, and the Nd?O bond in the complexes is highly covalent. The effect of the nature and constitution of the supported neodymium complexes on their activity in butadiene polymerization was studied. The copolymer was prepared in THF or dioxane was better for the synthesis of highly active supported complexes. Polymer-supported neodymium complexes containing about 12 wt% of -COOH gave optimum catalytic activity at a Nd/?COOH mole ratio of 0.20.     

Thermal Decomposition of Neodymium Amide Complexes

The decomposition of NdCl₃ L(L = N,N-dimethylformamide [DMF] or N,N-dimethyacetamide [DMA]) compounds has been investigated by thermogravimetric and differential thermal analysis (TGA and DTA) coupled with Fourier transform infrared (FTIR) spectroscopy. When heated in air, the NdCl₃L compounds decompose by a mechanism involving oxidation of the amide ligand to CO₂ and HCl. Some free armide is also released in the thermal decomposition in air. However, when heated under nitrogen, clean release of DMA or DMF is observed. In both cases, the amide is released two steps. From 30 to 40% of the amide is initially released with little or no associated enthalpy as measured by DTA. As the temperature is increased, the remaining 60 to 70% of the amide is released via an endothermic process. The enthalpy for this release is 53.1 - 3.8 kJ/mole for DMF and 40.9 - 1.1 kJ/mole for DMA, suggesting that DMF binds more strongly to Nd(III) than does DMA. Steric effects caused by the additional methyl group in DMA might be responsible for the weaker binding of this amide compared to DMF.     

The Synthesis of Neodymium Complexes with Polymers Containing Thiol and Sulphoxide and Their Catalytic Activities

Introduction Polymers containing thiol and sulphoxide which have active—SH and—SO groups respectively, have wide application to biological, pharmaceutical, industrial and other chemical field and—SH and—SO groups are easy to form complexes with metals, so they have aroused an increasing interest of many authors. A large number of functional resins and corresponding metal complexes have been synthesized.     

茂基二苯胺基镱配合物催化甲基丙烯酸甲酯聚合

茂基二苯胺基镱配合物催化甲基丙烯酸甲酯聚合     

三种不同碳桥联双核茂钛配合物的合成及催化乙烯聚合研究

合成了3种不同结构的CnH₂n桥联双核茂钛配合物(CH₃)₂C[(C₅H₄)TiCl₂(C₅H₅)]₂(3),(CH₂)_n[(C₅H₄)TiCl₂(C₅H₅)]₂(6,n=3;7,n=4),并用1HNMR进行了表征.发现以甲苯为溶剂时,不仅提高了产率,而且有效地避免了副产物Cp₂TiCl₂的生成.研究了化合物7/MAO(甲基铝氧烷)催化乙烯聚合的反应,考察了反应条件对催化体系的影响.结果表明,催化活性随着n(Al)/n(Cat.)比的增大而提高,聚乙烯的分子量在n(Al)/n(Cat.)=500和50℃时达到最高值9.0102×10⁴;随着聚合时间的延长,催化活性下降,而产物分子量不断升高;随着温度的上升,50℃时催化活性和聚乙烯的分子量最高,分别为2.4074×10⁵gPE/(molTi·h)和6.8679×10⁴.随着桥联双核茂钛配合物碳桥的增长,催化活性增加,所得聚乙烯的分子量降低.