Polymeric Pd catalysts for the reduction of acetamidocinnamic acid azlactone and its solvolysis products

Pd complexes have been obtained from linear and cross-linked copolymers ofR,S-, R-, andS-1-(4-vinylphenyl)ethylamine (1) with styrene and divinylbenzene. Reduction of these compounds gave catalysts which were active in the reductive solvolysis of -acetaminocinnamic acid azlactone (2) and hydrogenation of the solvolysis products -acetamidocinnamic acid (ACA), its esters, and its 1-phenylethylamide. The catalysts showed no enantioselective properties in the reductive hydrolysis, but were more active than the catalyst obtained in the absence of the polymer (the monomeric analog). The use of polymeric catalysts has shown that, in reductive aminolysis, the chiral nucleophile plays the dominant part in determining the stereoselectivity of the reaction, rather than the chiral ligand of the catalytic complex. The polymer matrix stabilizes the low-valent state of the palladium in the complex. In the hydrogenation of ACA and its esters, the catalyst on the cross-linked polymer is much more active than its monomeric analog, but showed no enantioselectivity. Hydrogenation of acetamidocinnamic acidR-andS-1-phenylethylamides on a chiral Pd-polymer catalyst occurred with double asymmetric induction.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2368–2380, October, 1992.     

Carboxylation of styrene in the N(C4H9)4Br—heptane system

The carboxylation of styrene into carboxylic acids in the N(C₄H₉)₄Br—heptane system in the presence of phosphine complexes and palladium acetate was studied. In the absence of phosphine, the Pd catalyst seems to be stabilized in solution by forming anionic complexes with NBu₄Br; the stabilization depends on the acidity of the reaction medium. The catalytic system can be used repeatedly, its activity being reduced only slightly.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2458–2461, November, 2004.     

Surface solid-state interactions in copper-nickel-cement catalysts for hydrogenation of oxygen

The surface phase composition of alumocalcium cement-supported CuO and CuO-NiO catalysts prepared by chemical mixing has been studied using the method of thermo-vacuum curves of electric conductivity. The deactivation of these catalysts due to overheating to 800 °C under conditions of hydrogenation of oxygen is rationalized by the partial extraction of CuO (and NiO) from the stabilizing structure of the support solid solutions and by sintering of the extracted oxides and the reduced metallic phase. Complete regeneration of the CuO-NiO-talum catalysts can be achieved if a considerable amount (20%) of copper hydroxocarbonate is added.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1559–1562, September, 1994.     

固体磷酸催化剂的活性相

研究了固体磷酸催化剂活性与其自由磷酸聚合态及磷酸硅晶型的关系，指出高活性磷酸催化剂应具备的条件，即自由磷酸中应为正磷酸和焦磷酸的混合物，结合态磷应具有“Ｃ”晶型。     

CO Oxidation on Cu/MgO-SiO2 Sol-Gel Derived Catalysts

Sol-gel Cu//MgOSiO₂ catalysts were prepared gelling tetraethoxysilane (TEOS), magnesium ethoxide and copper acetylacetonate at pH 3 and pH 9. The catalysts shown specific surface areas ca. 500 m²/g and 140 m²/g for pH 9 and pH 3 preparations respectively. Si(OH) and Si(OH)₂ hydroxy groups were observed by MAS-RMN spectroscopy in both preparations. CO₂-TPD and NH₃-TPD desorption thermograms showed that acid and basic sites were formed on the catalysts surface. It has been found that the catalysts having the highest density of basic sites were the catalysts showing the highest activity for the CO oxidation. It is proposed that the catalytic activity depends of the relative Cu⁼¹/Cu⁼² stability given by the support acidity.     

Thermal latency of novel chelating borate catalysts as latent catalysts for epoxy–phenolic resins

Novel quaternary ammonium bis(2‐oxybenzoyloxy)borate salts ( 1a – 1c ) or quaternary ammonium bis(1,2‐benzenedioxy)borate salts ( 2a and 2b ) with tetra‐n‐butylammonium (TBA⁺), tetra‐n‐octylammonium (TOA⁺), or bis(triphenylphosphoranylidene)ammonium (PNP⁺) cations were synthesized as latent catalysts of epoxy/phenol–novolac resins by the complexation between boric acid and salicylic acid or catechol, followed by neutralization with quaternary ammonium hydroxide. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with 1a – 1c in diglyme at 150 °C for 6 h proceeded up to 85–96% conversions and gave polymers with number‐average molecular weights of 4180–10,500, whereas the polyaddition at 80 °C for 6 h gave less than 8% conversions. However, the polyaddition with 2a containing TBA⁺ cation proceeded to only a 32% conversion at 150 °C for 6 h in diglyme and to a 64% conversion even at 180 °C for 6 h in triglyme and only gave low molecular weight oligomers, and no reaction proceeded in the polyaddition at 80 °C. However, polyaddition with 2b containing PNP⁺ cation proceeded up to a 96% conversion at 150 °C for 6 h in diglyme and gave a higher molecular weight polymer with a number‐average molecular weight of 8050, whereas the polyaddition at 80 °C for 6 h gave only a 5% conversion. The catalytic activity of ammonium borates 1a – 1c and 2a and 2b depended on the borate anion structure: 1a and 1c with bis(2‐oxybenzoyloxy)borate anion revealed higher activity than 2a and 2b with bis(1,2‐benzenedioxy)borate anion, respectively. In comparison with tetra‐n‐butylammonium bromide (TBAB) as a conventional ammonium salt or tetra‐n‐butylammonium tetrakis(benzoyloxy)borate (TBA‐TBB), 1a – 1c and 2b revealed better thermal latency. The catalytic activity of ammonium borates also depended on the bulkiness of the ammonium cation, and the order of activity was 1c (PNP⁺) > 1b (TOA⁺) ≧ 1a (TBA⁺) and 2b (PNP⁺) > 2a (TBA⁺). The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts 1a – 1c and 2a and 2b in bulk at 40 °C was much better than that with TBAB and TBA‐TBB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2702–2716, 2002     

Effect of iron-containing catalysts on thermal decomposition of cured GAP-AP propellants

The effects of various burning rate catalysts on thermal decomposition of cured glycidyl azide polymer (GAP)-ammonium perchlorate (AP) propellants have been studied by means of thermal analysis and a modified vacuum stability test (MVST). Four types of iron-containing catalysts examined in this paper are catocene, ferrocenecarboxaldehyde (FCA), ferrocene, and ferric oxide. Results of differential thermal analysis (DTA) and thermogravimetric analysis (TG) revealed that the catalysts play an important role in the decomposition of both AP and GAP. The peak decomposition temperature (T _m) of DTA curves and onset decomposition temperature (T _o) of TG patterns considerably shifted to a lower temperature as the concentration of catalysts increased in the propellants. The endothermic temperature of AP, however, is unaffected by the presence of burning rate catalysts in all cases. The activation energy of decomposition of the propellants in range of 80 to 120°C is determined, based on the MVST results.     

EFFECT OF MOLYBDENUM PROMOTER ON THE Cu-Co BASED CATALYSTS

The synthesis of mixed alcohols (C1-C5) from syngas has been studied at 6. 0 MPa over modified Co/CuLaZr catalysts. The molybdenum addition enhanced greatly the activity and the selectivity to alcohols. The improvement of hydrogenation capacity of the system via a reversible spillover effect of hydrogen could explain this effect, together with a great capacity of CO insertion, illustrated by the effect of C2H4 addition as a probe to syngas. Under our experimental conditions, a mixed alcohol production of 147.1g/kg. cat/h containing a proportion of 33. 1% of higher alcohols (C2 OH) was obtained with a selectivity to ROH of 52. 8%.     

Effect of silica-type sol-gel carrier’s structure and morphology on a supported Ziegler-Natta catalyst for ethylene polymerization

Silica xerogels with different structures and morphology, synthesized using a sol-gel procedure, were used as a carrier of vanadium catalysts (VOCl₃/AlEt₂Cl) for ethylene polymerization. Two techniques of catalyst synthesis were applied: slurry impregnation and gas-phase adsorption and the relevant polymerization methods were then employed. The effect of the carrier structure and morphology on the vanadium loading in the catalysts, the catalyst’s activity and kinetic stability were investigated.     

探究Cu/ZnO相互作用对CO2加氢制甲醇反应性能的影响

Using renewable green hydrogen and carbon dioxide (CO₂) to produce methanol is one of the fundamental ways to reduce CO₂ emissions in the future, and research and development related to catalysts for efficient and stable methanol synthesis is one of the key factors in determining the entire synthesis process. Metal nanoparticles stabilized on a support are frequently employed to catalyze the methanol synthesis reaction. Metal-support interactions (MSIs) in these supported catalysts can play a significant role in catalysis. Tuning the MSI is an effective strategy to modulate the activity, selectivity, and stability of heterogeneous catalysts. Numerous studies have been conducted on this topic; however, a systematic understanding of the role of various strengths of MSI is lacking. Herein, three Cu/ZnO-SiO₂ catalysts with different strengths of MSI, namely, normal precipitation Cu/ZnO-SiO₂ (Nor-CZS), co-precipitation Cu/ZnO-SiO₂ (Co-CZS), and reverse precipitation Cu/ZnO-SiO₂ (Re-CZS), were successfully prepared to determine the role of such interactions in the hydrogenation of CO₂ to methanol. The results of temperature-programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS) characterization illustrated that the MSI of the catalysts was considerably affected by the precipitation sequence. Fourier transform infrared reflection spectroscopy (FT-IR) results indicated that the Cu species existed as CuO in all cases and that copper phyllosilicate was absent (except for strong Cu-SiO₂ interaction). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and N₂O chemical titration results revealed that strong interactions between the Cu and Zn species would promote the dispersion of Cu species, thereby leading to a higher CO₂ conversion rate and improved catalytic stability. As expected, the Re-CZS catalyst exhibited the highest activity with 12.4% CO₂ conversion, followed by the Co-CZS catalyst (12.1%), and the Nor-CZS catalyst (9.8%). After the same reaction time, the normalized CO₂ conversion of the three catalysts decreased in the following order: Re-CZS (75%) > Co-CZS (70%) > Nor-CZS (65%). Notably, the methanol selectivity of the Re-CZS catalyst was found to level off after a prolonged period, in contrast to that of Co-CZS and Nor-CZS. Investigation of the structural evolution of the catalyst with time on stream revealed that the high methanol selectivity of the catalyst was caused by the reconstruction of the catalyst, which was induced by the strong MSI between the Cu and Zn species, and the migration of ZnO onto Cu species, which caused an enlargement of the Cu/ZnO interface. This work offers an alternative strategy for the rational and optimized design of efficient catalysts.