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1.
This paper describes the polymerization of acetylene by coordination catalysts composed ofvarious neodymium compounds, (Nd (P_(204))_3; Nd (P_(507))_3; Nd (NO_3)_3 3P_(350); Nd (BA)_3.2H_2O; andNd (acac)_3.2H_2O), aluminum trialkyl and an electron donor. The catalysts show fairly high catalyticactivity and high cis stereospecificity on acetylene polymerization at 30℃. 相似文献
2.
SOLUBLE POLYACETYLENE OBTAINED WITH RARE-EARTH CATALYST AND SOME ASPECTS OF POLYMERIZATION MECHANISM
Soluble polyacetylene (PA) with well--defined nature has been synthesized with catalyst system Nd(i-OPr)_3/AIR_3 (R=C_2H_5-, i-C_4H_9-) and characterized by IR, Raman and ESR Spectra etc. Number average molecular weight of the soluble specimen were determined by VPO to be about 500g/mol. or lower. The IR and NMR spectra and end group analysis of" the soluble polyacetylene fully demonstrate that polymerization of acetylene with rare-earth catalyst is realized through monomer insertion between the transition metal-carbon bond. 相似文献
3.
This paper is the first study on the stereospecific polymcrization of acetylene by coordination catalysts based on rare-earth compounds. High cis (80-100%) polyacetylene films with silvery metallic appearance were obtained at 30℃ or 0℃ in the presence of rare-earth catalysts composed of two or three components: naphthenates or 2-ethyl hexyl phosphonates of all fifteen rare-earth elements, trialkyl aluminum and/or a third component. The resultant polyacetylene has been characterized using techniques of infrared spectrophotometry, differential scanning calorimetry, electron spin resonance, X-ray diffraction, scanning electron micrography and electrical resistivity measurements. 相似文献
4.
Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-average molecular weights (M_W ) of PPSQ had beenmeasured by gel permeation chromatography (GPC). Effects of polymerization conditionsincluding reaction temperature, composition of the dual catalysts (CaF_2 or MgF_2 and DCC),mixture of solvents and reaction time on M_W of PPSQ have been discussed. The quantity of thecatalysts is the most important factor that affects M_W of PPSQ. Reaction temperature is thesecond important factor. Appropriate polymerization condition has been established to get PPSQwith high M_W. 相似文献
5.
The study on coordination copolymerization of styrene (S) with maleic anhydride (MA) by rare-earth coordination catalysts, NdL_3-Al(i-Bu)_3, has been successfully carried out for the first time. Some features, kinetic behavior, and mechanism of the SMA copolymerization by Nd(naph)_3-Al(i-Bu)_3 system are described and discussed. The copolymex of styrenemaleic anhydride prepared by the NdL_3-Al(i-Bu)_3 systems in benzene at 50℃ is an alternating-rich white powder having high number-average molecular weight of 6—8.5×10~5. The overall activation energy for the polymerization was found to be 10.5KJ/mol. The polymerization was not suppressed by addition of hydroquinone. The catalytic activity of various ligands in NdL_3 for the copolymerization decreases in the following order: Nd (naph)_3>Nd-(P_(507))_3~NdCl_3-6H_2O>Nd(P_(204))_3>Nd(acac)_3. 3H_2O. The experimental results are explained based on a mechanism to be the coordination-type copolymerization in terms of the participation of a monomer-monomer c 相似文献
6.
To address the issue of hemilabile catalyst in olefin polymerization catalysis, a cyclizing strategy was used to construct novel N-bridged phosphine-carbonyl palladium and nickel catalysts, resulting in improvements on ethylene(co)polymerizations. The N-bridged phosphinecarbonyl Pd catalysts(Pd1-Pd5) and Ni catalysts(Ni1-Ni5) bearing five-to eight-membered-ring structures were designed and synthesized.Catalytic performance for ethylene(co)polymerization became better as the size of N-containing bridge increased. The seven-membered-ring bridged catalysts Pd4 and Ni4 exhibited the best performance in terms of catalytic activity, polymer molecular weight and incorporation of acrylates and acrylic acid. The better performance of these catalysts bearing larger-size bridges was tentatively attributed to the methyleneinduced higher electron density around nitrogen, which strenghtens the coordination of carbonyl group to metal center, and also to the steric effect offered by this cyclization. This work provides a new strategy to enhance hemilabile polymerization catalysts. 相似文献
7.
《高等学校化学研究》1986,(1)
Catalytic polymerization of acetylene in the presence of n5-C5H5-M-(CO)3 R (M=Mo,W;R=CH3-,C2H5-) has been studied.The results show that these complexes possess catalytic activities for the polymerization and copolymerization of monosubstituted acetylene.The catalytic mechanism has been preliminarily discussed.It is suggested that the active species be metal-car-bene.In our previous publications we reported the synthesis of some new Fischer's molybdenum and tungsten-carbene complexes and catalytic activity for alkyne polymerization.The results show that the activity of Fischer's molybdenum-carbene is higher than that of tungsten.The catalytic polymerization of alkyne by M-σ-c bond-containing complexes of molybdenum and tungsten has not been reported yet in literature.Therefore,four M-σ-C bondontaining complexes of molybdenum and tungsten were synthesized by using the method reported in the literature,and catalyst polymerization of alkyne by these complexes was examined. 相似文献
8.
《分子催化》1989,(Z1)
The surface characteristics and catalytic activity of Sb_xO_Y/ SiO_2 catalysts forvapor-phasc synthesis of isoprene from isobutylene and formaldehyde have been investi-gated by TPR, XRD, XPS, IR and catalytic activity evaluation. The results show that whenthe Sb loadings are less than about 5 wt%,Sb_xO_Y is compIctely dispersed on the surface ofsilica to form a surface compound with Sb(V)=O group and the catalysts have relativelyhigh catalytic activity; when the Sb loadings are more than 5 wt%, in addition to this surfacccompound, the crystalline α-Sb_2O_4 is formed on the support surface and causes rapid de-crease of catalytic activity. It is suggcsted that the catalytic activity of Sb_xO_Y /siO_2 catalystsresults from synetgistic catalysis of the surface compound Sb(V)=O as the basic sites andthe surface silanol Si-OH as the acidie sites. The mechanism of this synergistic catalysis forisoprene production is discussed. 相似文献
9.
<正>Rare earth aryloxides substituted by various alkyl groups[Ln(OAr)_3]such as methyl,isopropyl and tertbutyl,were used as single component catalysts to affect ring-opening polymerization of L-lactide(LLA).The catalytic activity, polymerization characteristics,polymerization kinetics and the mechanism were studied.It was found that the catalytic activity of rare earth aryloxides is influenced by both the structure and the number of alkyl groups on the phenyl ring.The stronger the electron-donation ability of the alkyl group,the higher the catalytic activity will be.An increase in the number of the substitute group will result in a higher catalytic activity.Lanthanum tris(2,4,6-tri-tert-butylphenolate)[La(OTTBP)_3] exhibits the highest activity among all lanthanum aryloxides.According to the ~1H-NMR data,it was proposed that the LLA polymerization proceeded via a coordination-insertion mechanism involving cleavage of acyl-oxygen bond of the lactide. 相似文献
10.
G.B.Aldashukurova A.V.Mironenko Z.A.Mansurov N.V.Shikina S.A.Yashnik V.V.Kuznetsov Z.R.Ismagilov 《天然气化学杂志》2013,(5):811-818
The catalytic activity of nanostructured low percent (1%) Co-Ni catalysts on the basis of glass fiber (GF) prepared by a"solution combustion" (SC) method was studied.The catalytic activity of the prepared samples was studied in the reaction of dry reforming of methane (DRM) with CO2.The obtained samples were characterized by a number of physico-chemical methods,including XRD,SEM,TEM,TGA and AFM.The active component was shown to be dispersed in the near-surface layer of the support as nanoparticles of 10—20 nm in size.The active component showed a Co3O4 or(Co,Ni)Co2O4 spinel structure,depending on the catalyst composition.The spinel structure of the active component interacted strongly with the carrier,providing resistance to carbonization,high catalytic activity toward DRM,and high activity and stability in oxidation reactions. 相似文献