共查询到18条相似文献,搜索用时 109 毫秒
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本文综述了我国首创开拓的稀土络台催化聚合在炔烃和开环聚合方面的新进展.用稀土络合催化剂可以使乙炔、苯乙块在室温下聚合制备高顺式含量和抗氧化稳定性良好的聚炔烃膜;可以使环氧乙烷、环氧丙烷、环氧氯丙烷和环硫丙烷聚合制备高分子量聚合物;可以使丙交酯聚合制备可控分子量聚合物. 相似文献
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稀土催化四氢呋喃开环聚合 总被引:5,自引:0,他引:5
1937年Meerwein首次发现Et_3O~(+BF)可催化四氢呋喃(THF)开环聚合。到目前为止,发现能使THF开环聚合的催化剂有质子酸、Lewis酸、洋离子、正碳离子等。1990年吴健等将(Acac)_3Nd-(i-Bu)_3Al-H_2O-环氧氯丙烷催化体系应用于THF聚合,发现它和(i-Bu)_3Al-H_2O-环氧氯丙烷体系具有相同的活性,这说明稀土配合物没有参与活性中心的形成。本工作发现(CF_3CO-2)3Ln(Ln=Y,La,Ce, 相似文献
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稀土络合催化环氧乙烷聚合 总被引:3,自引:1,他引:3
以稀土化合物-二(2-乙基己基)膦酸钕[Nd(P_(204)_3],三异丁基铝和水组成的络合催化剂,引发环氧乙烷聚合.结果表明,稀土络合催化剂是制备高分子量聚环氧乙烷的新型催化剂.聚合反应速度与环氧乙烷浓度呈一级关系,与Nd(P_(204))_3浓度呈一级关系.聚合的总活化能E_α=33.8kJ/mol,表观速率常数K_p=1.67×10~(-3)s~(-1)·mol~(-1)·1 相似文献
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通过稀土氯化物与席夫碱钠盐的交换反应制备了一系列以 3,5-二叔丁基水杨醛缩苯胺为配体的稀土席夫碱配合物. 对其中的钕席夫碱配合物进行了 X射线单晶衍射分析, 发现其单晶结构为五角双锥构型, 所得席夫碱稀土配合物可以单组分催化 ?-己内酯开环聚合. 深入研究了钕席夫碱配合物催化己内酯的开环聚合机理, 考察了不同聚合条件对单体转化率、产物分子量及分子量分布的影响. 结果表明, 该聚合反应速率为一级, 聚合反应具有较好的可控性. 聚合物端基分析表明, 聚合反应以配位-插入机理进行. 相似文献
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稀土化合物催化内酯开环聚合 Ⅱ.异丙氧基稀土催化D.L-丙交酯开环聚合 总被引:8,自引:1,他引:8
系统地研究了异丙氧基稀土催化D.L-两交酯(LA)开环聚合的规律.实验表明:在甲苯溶剂中,异丙氧基稀土对D.L-丙交酯聚合有较高的催化活性,可获得较高的分子量(Mη=4.0×104)不同稀土元素的活性次序如下:La>Nd>Dy>Y.异丙氧基稀土催化D·L-两支酯聚合的合适条件为:[LA]=1.95mol/l,[Ln(O-i-Pr)3]=6.5×10-3mol/l,甲苯,90℃,聚合反应速度与单体和催化剂浓度均成一级关系,聚合反应表现活化能为着67.7kJ/mol. 相似文献
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RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS* 总被引:1,自引:0,他引:1
Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry. 相似文献
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(D, L)-Lactide (LA) was first polymerized with one component of rare earth cata-lysts [Nd(naph)_3, Nd(oct)_3, Nd(O-iPr)3, Nd(AcAc)_3, Y(AcAc)_3, Sm(AcAc)_3, Er(AcAc)_3)]respectively in solution and in melt state. The effects of [Cat]/[LA] molar ratio, solvents,polymerization time, temperature, various rare earth elements and ligands were investi-gated in detail. The results showed that both the conversion of polymerization and themolecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higherthan that in solution polymerization, but the polymerization rate in melt was lowr than insolution. The molecular weight distribution (MWD) of PLA is broader with increasing tem-perature. X-ray study indicated that PLA obtained by Nd(AcAc)_3 in melt polymerizationis an amorphous polymer. 相似文献
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KANG Hui-Min CHEN Bao-ShuWANG Da-Xiang KANG Xi-Hui ZHAO Jiu-ShengChemical Engineering Department Tianjin University Tuianjin 《天然气化学杂志》1995,(2)
Rare earth metals (RE metal ) such as La and Ce are selected aspromoters in the Cu-based low alcohol synthesis catalysts. Their effects on thecatalyst structure and performance are studied. Promoters La and Ce have thetrend to form a network-like structure on the catalyst surface with result ofstabilizing the Cu crystallites on it and prohibiting them from sintering at hightemperature. RE metal has also the property of compensating the decreasingeffect of promoter potassium on its surface area. As a result, the introductionof RE metul to the Cu-based low alcohol synthesis catalyst can improve itsthermal stability and increase its selectivity to C_2~ alcohols. 相似文献
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The copolymerization of l-octene with styrene catalyzed by rare earth coordination catalysts has been studied for the first time. Some features and kinetic behavior are described. The overall activation energy of the copolymerization was 22.2 KJ/mol and the copolymerization rate could be expressed as R_p=K_p [Nd] [M]~2. (=1.68×10~(-3) L~2/mol~2. S, 50℃, [Oct]/[St]=1). The catalytic activity of various rare earth elements in Ln (naph)_3 for the copolymerization was compared and shows the following sequence: Dy, Y, Yb>Ho>Sm, Gd, Nd>Pr>Ce>La>Tm. Both monomers of l-octene and styrene in the copolymerization by Nd (naph)_3-AlEt_3 have the tendency of constant proportion copolymerization. The structure of the copolymers was studied by ~1H-NMR. 相似文献