配体对二苯胺基稀土化合物催化丙烯腈聚合性能的影响

考察了 2 ,6 二叔丁基 4 甲基苯酚、乙酰乙酸乙酯、二亚甲基桥联二 (甲基环戊二烯 )三种配体对二苯胺基稀土化合物催化丙烯腈聚合性能的影响。结果表明 ,两种非茂类配体对促进稀土胺化物催化活性十分有限 ,桥联二茂基配体相对较好 ,但活性仍低于Ind2 LnN(i Pr) 2 。实验进行了温度、单体浓度、催化剂用量对丙烯腈聚合影响的研究。     

影响丙烯腈催化水合反应重要工艺条件的探讨

本文探讨了以丙烯腈(AN)为主要原料,在铜-铝合金催化剂的作用下、催化水合生产丙烯酰胺(AM)的工艺条件中,催化剂中铜-铝的组成比例、催化剂晶粒的大小、原料水的质量、原料水中的溶存氧和催化剂的活化再生条件对催化水合反应的影响。     

Ln_2O_3/MgO(Ln=Nd、Sm、Er)催化合成DOP、DOM和DOA

采用共沉淀—焙烧法制成的Ｌｎ２Ｏ３／ＭｇＯ（Ｌｎ＝Ｎｄ、Ｓｍ、Ｅｒ）担载型催化剂，由于比表面增大，分散性好。在催化合成ＤＯＰ、ＤＯＭ、ＤＯＡ中效果明显，且Ｌｎ２Ｏ３的用量下降８０％左右。     

Ln2O3/MgO催化合成增塑剂IOP的研究

采用共沉淀-焙烧法制成了LnO3／MgO(Ln=Nd，Sm，Er)担载型催化剂。该型催化剂比表面大，分散性好。在催化合成IOP中效果明显，且使Ln2O3的用量减少80％左右。     

Ln2O3／Al2O3催化合成内增塑剂DOM

采用共沉淀焙烧法制成的Ｌｎ２Ｏ３／Ａｌ２Ｏ３ 担载型催化剂,由于比表面大,分散性好,在催化合成ＤＯＭ 中效果明显。     

Ln(Ⅲ)-Cu(Ⅱ)-Ln(Ⅲ)异三核配合物的合成和性质

合成了三种新的异三核配合物，其组成为｛Ｌｎ２（ｂｐｙ）４〔Ｃｕ（ｏｐｂａ）〕（ＣｌＯ４）２｝（ＣｌＯ４）２。其中ｏｐｂａ表示邻苯双（草胺酸根）；ｂｐｙ表示２，２′－联吡啶；Ｌｎ表示Ｌａ、Ｎｄ、Ｔｂ。通过元素分析、红外光谱、紫外光谱、差热－热重及摩尔电导分析等手段，表征了配合物。     

两种丙烯酸盐[Ln2(CH2CHCOO)6·3H2O]·3H2O(Ln=Ce;Nd)的单晶结构

采用X射线单晶衍射法,解析了[Ln2(CH:CHCOO)6·3H2O]·3H2O(Ln=Ce;Nd)的结构.结果表明标题化合物属同构:属单斜晶系(空间群P2(1)/c);[Ce2(CH2CHCOO)6·3H2O]·3H2O晶胞参数α=1.02099(13)nm,b=1.52294(19)nm,c=2.0325(3)nin,/3=100.838(2)°,V=3.1039(7)nm3;[Nd2(CH2CHCOO)6·3H2O]·3H2O晶胞参数α=1.01978(8)nm,6=1.50979(12)nm,c=2.02712(16)nm,β=100.881(1)°,V=3.0650(4)nm3.化合物不对称结构单元中含有两个独立的稀土中心离子,分别处九、十配位环境中.两个稀土离子由两个独立的丙烯酸μ2-氧桥联形成左手和右手螺旋链.螺旋链通过链间的水分子形成氢键网络,堆垛成三维结构.     

添加剂对硬质合金性能的影响

本文综述了向硬质合金中加入稀土元素、金属和金属碳化物对硬质合金性能的影响。指出添加稀土元素的硬质合金由于性能好,使用范围广,有着很好的发展和应用前景。     

Ln2O3／X—13分子筛作酯化反应催化剂的研究

用浸渍-焙烧法制备的Ln2O3／X－13分子筛（Ln＝Nd、Sm、Tm、Lu、Eu、Dy），其稀土氧化物含量为0．83％～0．93％，该分子筛对芳香酸、脂肪酸与醇的酯化反应有明显的催化作用．芳香酸酯化反应转化率以合成邻苯二甲酸二辛酯（DOP）为例，它比无催化剂的转化率提高10％左右，比X－13分子筛的催化转化率提高8％左右；脂肪酸酯化反应转化率以合成棕酸辛酯（IOP）为例，它比无催化剂的转化率提高7％左右，比X－13分子筛的催化转化率提高4％左右．而且，Ln2O3／X－13分子筛与Ln2O3／Al2O3型酯化反应催化剂相比，其稀上用量下降25％左右．酯化反应温度下降10℃左右．上述结果表明．Ln2O3／X－13分子筛是一种优良的酯化反应催化剂。     

Nd2O3催化聚合松香酯化反应的动力学研究

研究了氧化钕、氧化钐、氧化钆、纳米氧化镧和纳米氧化铈等5种稀土氧化物催化聚合松香酯化反应的活性,Nd2O3催化聚合松香与辛醇、乙二醇和甘油进行酯化反应的动力学.结果表明,所选5种稀土氧化物均能有效地催化聚合松香的酯化反应,其中Nd2O3的催化效果最佳.在醇过量的条件下,Nd2O3催化聚合松香与辛醇、乙二醇和甘油的酯化反应是受界面化学反应扩散控制的一级反应,其动力学方程分别为k=2.74×105e-58087/RT、k=6.78×105e-60957/RT和k=8.11×106e-69279/RT.随着脂肪醇元数的增加和结构的复杂化,聚合松香酯化反应的表观活化能随之增大.     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb（NPh2）3（THF）2

A neutral homoleptic lanthanide amide Yb(NPh2)3(THF)2 was obtained by reaction of anhydrous YbCl3 with LiNPh2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P21/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm3, Z=4, Dc=1.417 g*cm-3, μ=24.67 cm-1 (Mo Kα), F(000)=1668, R=0.036, Rw=0.039. The central metal ytterbium is coordinated by three terminal NPh2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.     

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb(NPh_2)_3(THF)

Ｌａｎｔｈａｎｉｄｅａｍｉｄｅｃｏｍｐｌｅｘｅｓａｒｅａｎｉｍ ｐｏｒｔａｎｔｃｌａｓｓｏｆｐｒｅｃｕｒｓｏｒｓｆｏｒｌａｎｔｈａｎｉｄｅｄｅｒｉｖａｔｉｖｅｓ .Ｉｔｃａｎｂｅｅａｓｉｌｙｔｒａｎｓｆｏｒｍｅｄｔｏｃｏｒ ｒｅｓｐｏｎｄｉｎｇｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｂｙｒｅａｃｔｉｎｇｗｉｔｈｉｎｖｏｌｖｉｎｇｐｒｏｔｉｃｒｅａｇｅｎｔｓ[1,2 ] .Ｔｈｅｌａｎｔｈａｎｉｄｅａｍｉｄｅｕｓｅｄａｓｓｙｎｔｈｅｔｉｃｐｒｅｃｕｒｓｏｒｉｓｎｅｕｔｒａｌｈｏｍｏｌｅｐｔｉｃｃｏｍｐｌｅｘ ,ｏｔｈ…     

Synthesis, Characterization and Thermal Decomposition of Ln (Me2dtc)3(phen) (Ln=La, Pr, Nd, Sm)

Four solid complexes of Ln(Me2dtc)3(phen) (Ln=La, Pr, Nd, Sm) were synthesized in anhydrous ethanol by the reaction of lanthanide chloride low hydrate with the mixed ligand of sodium dimethyldithiocarbamate and 1, 10-phenanthroline·H2O (phen·H2O), and characterized by elemental analysis, IR spectroscopy, TG-DTG, and X-ray diffraction analysis. TG-DTG with X-ray powder diffraction showed that these compounds could decompose to lanthanide sulfides at relatively lower temperature, which indicated that the title complexes could be favorable precursors to prepare lanthanide sulfides.     

Polymerization of Acrylonitrile with （Diisopropylamido） Bis（indenyl） Lanthanides

Ｔｈｅｒｅａｒｅａｌｏｔｓｏｆｒｅｐｏｒｔｓａｂｏｕｔｔｈｅｐｏｌｙ ｍｅｒｉｚａｔｉｏｎｏｆａｃｒｙｌｏｎｉｔｒｉｌｅ (ＡＮ) [1～ 3] .Ｉｎｔｈｅｒａｄｉｃａｌｐｏｌｙｍｅｒｉｚａｔｉｏｎ ,ｕｓｕａｌｌｙｉｔｉｓｉｎｉｔｉａｔｅｄｂｙｂｅｎｚｏｐｅｒｏｘｉｄｅ ,Ｋ2 Ｓ2 Ｏ4 Ｎａ2 Ｓ2 Ｏ3,Ｆｅ2 + Ｈ2 Ｏ2 ａｎｄｓｏｍｅｏｒｇａｎｉｃｃｏｍｐｏｕｎｄｓ .Ｔｈｅｒｅ ｐｏｒｔｓｏｎｏｒｇａｎｏｌａｎｔｈａｎｉｄｅｓａｓｓｉｎｇｌｅ ｃｏｍｐｏｎｅｎｔｃａｔａｌｙｓｔｓｗａｓｒａｒｅｌｙｉｎｌｉｔｅｒａ…     

Synthesis and Characterization of Ln(NO_3)_3-Phen-Fu Ternary Complexes

ＳｙｎｔｈｅｓｉｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＬｎ（ＮＯ３）３ＰｈｅｎＦｕＴｅｒｎａｒｙＣｏｍｐｌｅｘｅｓＬｉｎＪｉｙｕｎ（林纪筠），ＭａＤｅｊｉａｎ（马德建）（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＥａｓｔＣｈｉｎａＮｏｒｍ...     

Catalytic Action of Ln（η^6-C6H6） （AlCl4）3 in Alkylation of Benzene

The alkylation of benzene with 1-hexene which gives 1-phenylhexane and 2-phenylhexane were achievedunder mild conditions by use of neutral π-arene complex of lanthanide Ln(η6-C6H6) (AlC14)3. The effect of Ln( η6-C6H6)(A1C14)3 and reaction conditions on the alkylation reaction were studied.     

Synthesis of the Early Lanthanide Complexes[Li(DME)_3][MeCpLn(NPh_2)_3](Ln=La,Pr,Nd)and X-Ray Crystal Structure of La Complex

The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane andtoluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)byextraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complexcrystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm,β=96.04°,V=5.277 nm~2,Z=4,D_c=1.26g·cm~(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec-tions.The complex consists of a pair of a cation and an anion.La~(3+) is coordinated by onemethylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the meanLn-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.     

Spectroscopic investigations on the effect of humic acid on the formation and solubility of secondary solid phases of Ln_2（CO_3）_3

The formation of secondary Ln(III) solid phases (e.g., Nd2(CO3)3 and Sm2(CO3)3) was studied as a function of the humic acid concentration in 0.1 mol/L NaClO4 aqueous solution in the neutral pH range (5-6.5). The solid phases under investigation were prepared by alkaline precipitation under 100% CO2 atmosphere and characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), time-resolved laser fluorescence spectroscopy (TRLFS), diffuse reflectance ultraviolet-visible (DR-UV-Vis), Raman spectroscopy, and solubility measurements. The spectroscopic data obtained indicated that Nd2(CO3)3 and Sm2(CO3)3 were stable and remained the solubility limiting solid phases even in the presence of increased humic acid concentration (0.5 g/L) in solution. Upon base addition in the Ln(III)-HA system, decomplexation of the previously formed Ln(III)-humate complexes and precipitation of two distinct phases occurred, the inorganic (Ln2(CO3)3) and the organic phase (HA), which was adsorbed on the particle surface of the former. Nevertheless, humic acid affected the particle size of the solid phases. Increasing humic acid concentration resulted in decreasing crystallite size of the Nd2(CO3)3 and increasing crystallite size of the Sm2(CO3)3 solid phase, and affected inversely the solubility of the solid phases. However, this impact on the solid phase properties was expected to be of minor relevance regarding the chemical behavior and migration of trivalent lanthanides and actinides in the geosphere.     

Mechanochemical Effects in Ln_2O_3-Ln(OH)_3-(H_2O)(Ln=La,Nd) System

ＭｅｃｈａｎｏｃｈｅｍｉｃａｌＥｆｅｃｔｓｉｎＬｎ２Ｏ３Ｌｎ（ＯＨ）３（Ｈ２Ｏ）（Ｌｎ＝Ｌａ，Ｎｄ）ＳｙｓｔｅｍＤｉｍｉｔｒＴｏｄｏｒｏｖｓｋｙ，ＡｔａｎａｓＴｅｒｚｉｅｖ（ＦａｃｕｌｔｙｏｆＣｈｅｍｉｓｔｒｙ，ＵｎｉｖｅｒｓｉｔｙｏｆＳｏｆｉａ...