共查询到20条相似文献,搜索用时 46 毫秒
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高分子铑配合物(PYBRh)催化甲醇羰基化为乙酸和乙酸酐的动力学研究 总被引:4,自引:1,他引:4
采用2-乙烯吡啶-丁烯酮共聚物为配体,与四羰基二氯二铑形成顺二羰基铑(I)配合物(PYBRh),用于催化甲醇羰基化制备乙酸和乙酸酐的反应动力学研究。结果表明,其对反应物甲醇和一氧化碳均为零级反应,在一定范围内,对高分子铑催化剂及助催化剂碘甲烷均为一级反应,极性溶剂的加入可以提高甲醇羰基化速度。通过实验结果计算了其反应活化能,活化熵和热焓研究证明其反应机理与小分子铑催化剂相似。 相似文献
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A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions. 相似文献
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Naomichi Furukawa Toshiaki Yoshimura Shigeru Oae 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):277-280
Abstract Methyl phenyl N-p-tosylsulfilimine was found to undergo Pummerer type rearrangement affording α-acetoxymethyl phenyl sulfide similar to the corresponding sulfoxide. In order to clarify the mechanism of the reaction of methyl p-substituted phenyl sulfilimines with acetic anhydride, kinetic experiments were carried out. A large negative value of activation entropy, a relatively small value of activation enthalpy and the influence of acetic acid seem to reveal that the initial intermediate, i.e., acetylated sulfilimine, receives the nucleophilic attack of acetate ion to replace imino group, and this substitution reaction is the rate determining step. 相似文献
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采用以原子重叠及电子离域的分子轨道理论ASED MO(含原子对排斥的EHMO法)为基础的结构自动优化法,对共聚物铑配合物催化甲醇羰基化制乙酸反应速率控制步骤 氧化加成进行了理论研究.计算了不同共聚物配体形成的铑催化剂与碘甲烷的氧化加成反应途径,并得到反应活化能,分析了氧化加成反应过程中的电子转移和空间因素对活化能的影响,计算结果与实验结果是相符的,并从理论上解释了2 乙烯基吡啶形成的共聚物铑配合物催化活性高于4 乙烯基吡啶形成的共聚物铑配合物催化活性的原因. 相似文献
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Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodiumused as a catalyst for carbonylation of methanol to acetic acid and anhydride has beenstudied. The structural characteristics of the copolymer ligand and complex, and the in-fluences of the reaction conditions on the carbonylation catalyzed by this polymer complexhave been investigated. In comparison with small molecule catalyst of Rh complex, thebidentate copolymer coordinated complex has better thermal stability. The reactionmechanism of the carbonylation reaction is also illustrated. 相似文献
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共聚物铑配合物催化甲醇羰基化制备醋酸的反应动力学分析 总被引:4,自引:1,他引:4
以共聚物铑配合物催化甲醇羰基化经醋酸甲酯到醋酸的反应,具有高稳定性、高活性的特点.本文通过对作者近期研究工作的总结,绘出此催化反应全过程的循环图,并在此基础上求出有关动力学参数,结果计算值与实验值相符,证明此机理的合理性,并讨论了几种共聚物配体之间的差异. 相似文献
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Er2(PhCH2COO)6·4H2O的结构及热分析 总被引:1,自引:0,他引:1
用X-射线四圆衍射仪测定了Er_2(PhCH_2COO)_6·4H_2O的晶体结构。配合物属于单斜晶系, 空间群为P2_1/α, 晶胞参数:α=0.9008(3) nm, b=1.4243(5) nm, c=1.8437(7) nm, β=98.80(3)°, V=2.337(1) nm~3, Z=4. 采用TG-DTG-DTA研究了配合物的热分解过程, 确定了热分解机理。采用Freeman-Carroll方法计算了配合物脱水过程的活化能和反应级数。用DSC测定了配合物脱水, 熔化过程的焓变。 相似文献
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Abstract— By dual wavelength absorption spectroscopy and fluorimetry. a flavin photo-redoxcycle never reported before has been observed in solvents composed of alcohols (methanol, ethanol, benzyl alcohol) and acetic acid. This cycle consists of a fast anaerobic photoreduction with a subsequent rcoxidation of the flavin as a dark reaction. The photoreduction process is not sensitive to the prescnce of water (up to 50 vol%), in contrast to the reoxidizing process, which is completely inhibited by 10 vol% of water. Furthermore. this photocycle is inhibited by esters. Negative activation energies of about 20 kJ/mol for both photoreduction and oxidation indicate complex molecular mechanisms. It is proposed that photoreduction of the flavin produces a highly volatile oxidizing agent responsible for the subsequent reoxidation. Photoreducing and oxidizing species remain to be identified. 相似文献
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Abstract A method is presented for preparing dimethylphosphinyl acetic acid by carboxylation of trimethylphosphine oxide α-carbanion. The product from this simple one step reaction is easily purified by extraction and ion exchange chromatography. 相似文献
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The complex resins prepared from macroporous sulfonated resin D72(H^+ form) with ferric chloride or ferric chloride hexahydrate have both sites of Bronsted acid and Lewis acid.In the catalysis of exterification of acetic acid with butanol the complex resins show to have much higher catalytic activity than that of its matrix.a conventional sulfonated cation exchange resin D72. 相似文献
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Hβ分子筛催化的甲苯与乙酸酐(AA)酰化反应研究 总被引:3,自引:1,他引:3
以Hβ分子筛为催化剂,对甲苯与乙酸酐(AA)的酰化反应进行了研究。通过研究反应温度、压力、甲苯与乙酸酐(AA)摩尔比、催化剂用量、以及溶剂的种类和用量等因素对反应转化率和选择性的影响,确定了较优的反应条件。结果表明,Hβ分子筛对甲苯与乙酸酐(AA)酰化反应具有较好的催化活性和选择性,适宜的反应条件为:温度130 ℃、甲苯/乙酸酐(AA)摩尔比20、催化剂/乙酸酐(AA)重量比0.8,极性溶剂如硝基苯等对酰化反应有一定的促进作用,但选择性有所下将,而非极性溶剂如二氧化碳可部分抑制催化剂的失活。 相似文献
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A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central
rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these
complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes
show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic
acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces
the investment on the equipment.
Project supported by the National Natural Science Foundation of China (Grant No. 29574186). 相似文献
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A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment. 相似文献
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