树脂担载金催化苯胺衍生物氧化羰化制氨基甲酸甲酯

树脂类高聚物担载的各种过渡金属和贵金属催化剂在加氢、选择氧化、聚合、氢甲酰化等反应中已有应用^[1,2],金催化剂作为一种新型的催化材料正日益引起人们的重视。继无机氧化物担载金催化剂得到广泛使用后^[3-7],有机金催化下的醇醛缩合^[8]、烯烃羧化^[9]以及锡烷偶联^[10]等反应的效果亦很好。最近,我们将有机金配合物催化剂用于胺类化合物氧化羰化制取氨基甲酯的反应^ [11],结果很好。但该均相催化体系仍存在催化剂分离回收和重复使用困难等问题。我们将金担载于各种高聚物上并用于苯胺及其衍生物的氧化羰化时,发现使用大孔弱酸性阳离子交换树脂作为催化剂载体对该反应的活性很高。相对于以往广泛研究的钯、钌、铑等的各种配合物加助催化组分催化剂体系^[12-14],这一体系简单、高效、易分离,且能够重复使用。     

CH4-CO2 reforming to syngas over Pt-CeO2-ZrO2/MgO catalysts: Modification of support using ion exchange resin method

Pt-CeO2-ZrO2/MgO (Pt-CZ/MgO) catalysts with 0.8 wt% Pt, 3.0 wt% CeO2 and 3.0 wt% ZrO2 were prepared by wet impregnation method. Support MgO was obtained using ion exchange resin method or using commercial MgO. XRD, BET, SEM, TEM, DTA-TG and CO2-TPD were used to characterize the catalysts. CH4-CO2 reforming to synthesis gas (syngas) was performed to test the catalytic behavior of the catalysts. The catalyst Pt-CZ/MgO-IE(D) prepared using ion exchange resin exhibits more regular structure, smaller and more unique particle sizes, and stronger basicity than the catalyst Pt-CZ/MgO prepared from commercial MgO. At 1073 K and atmospheric pressure, Pt-CZ/MgO-IE(D) catalyst has a higher activity and greater stability than Pt-CZ/MgO catalyst for CH4-CO2 reforming reaction at high gas hourly space velocity of 36000 mL/(g·h) with a stoichiometric feed of CH4 and CO2. Activity measurement and characterization results demonstrate that modification of the support using ion exchange resin method can promote the surface structural property and stability, therefore enhancing the activity and stability for CH4-CO2 reforming reaction.     

PEG grafted AM SURE™ resin and its application to solid-phase peptide synthesis

PEGylated core-shell type resin (PEG-AM SURE) was developed by modifying the surface of AM SURE™ resin with diamino PEG. The conditions for the PEG coupling reaction were optimized by adjusting PEG chain cross-linking and the amount of free amino groups to ensure a enough loading level of functional groups on the resin (>0.30-0.39 mmol NH₂/g). The resulting PEG-AM SURE resin showed better performance than conventional resins during solid-phase peptide synthesis of JR10-mer and β2m_58-69 12-mer.     

甲烷单加氧酶的模型化合物:以树脂为载体的双铁(Ⅲ)催化剂的合成、表征及催化性能的研究

使用树脂为载体,合成了6种新的双铁(Ⅲ)催化剂,成功的模拟了可溶性甲烷单加氧酶(MMO)的双核铁中心.这是首次使用树脂作为载体合成模拟MMO的非均相催化剂.在室温下以乙腈为溶剂,30%的过氧化氢或特丁基过氧化氢做氧化剂,环己烷或乙苯作为底物的反应中,催化剂具有MMO相似的催化活性.其中,使用大孔氨甲基树脂为载体合成的催化剂能有效地催化乙苯氧化得到较好的转化率(总收率达69.9%,TON值达55.3).同时研究了树脂的颗粒大小及阴离子供体对催化性能的影响.使用粒径0.675～0.280 mm的树脂和ClO-4的阴离子供体所合成的催化剂具有很好的催化活性.最后探讨了催化剂的回收和再利用.     

Palladium complex catalyst immobilized on epoxy support under supercritical conditions

The aim of this research was to obtain a new-generation complex catalyst under supercritical carbon dioxide. A new complex catalyst based on epoxy resin cured with multifunctional polythiourethane was prepared. The use of polythiourethane as a hardener allowed us to introduce linking groups into the structure of the polymer without further functionalization of the resin. Additionally, the use of supercritical CO₂ enabled a more accurate and better distribution of the metal complex in the polymer matrix. The presence of the functional groups allowed us to obtain a catalyst wherein the metal centers had a different electronic structure and various degrees of oxidation, so that such a system was characterized by its high selectivity. The catalytic properties of the prepared catalysts were tested in the hydrogenation reaction. Research methods like time-of-flight secondary-ion mass spectrometry (ToF–SIMS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and nitrogen BET surface area measurements were used to characterize polymeric support and heterogenized catalysts.     

Catalytic activity of an iron(III) Schiff base complex bound in a polymer resin

An iron(III)–ferrocene complex and its heterogeneous analogue bound in a polymer resin have been prepared and employed as catalysts for the oxidation of various organic substrates. Characterization of the heterogeneous and homogeneous complexes was done by SEM, EDAX, TGA, FT-IR, DRS-UV, and spectroscopy. The catalyst’s activity, stability, and reusability were investigated through industrially relevant oxidation reactions. The solid iron(III)–ferrocene Schiff base complex gave more effective results than the solid-supported ferrocene Schiff base ligand. The antimicrobial activities of the molecular complex and free ligand were studied for Gram-positive and Gram-negative bacteria.     

间苯二酚-甲醛树脂凝胶对Co/SiO_2催化剂费-托性能的影响(英文)

采用共沉淀法制备了高Co含量的Co/SiO2费托合成催化剂,并向其中添加一定含量的间苯二酚-甲醛树脂凝胶.结果表明,催化剂在393K干燥时,树脂会发生分解,因而仅有少量的含碳凝胶残留在催化剂中.然而,少量碳凝胶的存在显著增加了催化剂的还原度和金属钴的分散度,致使催化剂表面产生更多的活性金属Co,同时,催化剂的孔径也有所增大,因此Co/SiO2催化剂具有更高的反应活性及高碳烃选择性.其中80%Co/SiO2-C催化剂活性及高碳烃的选择性与我们前期报道的一种高活性的80%Co-8%ZrO/SiO催化剂相近.     

溶剂化金属原子浸渍法制备聚合物固载Co-Ag催化剂Ⅱ.催化性质研究

用溶剂化金属原子浸渍技术制备了高分散树脂固载Co -Ag双金属催化剂。研究了这些催化剂在二丙酮醇加氢和用作燃料电池电极时的催化性质。与普通浸渍法制备的相同组成的催化剂相比 ,溶剂化金属原子浸渍催化剂显示出更高的活性。这是因为溶剂化金属原子浸渍催化剂具有更高的分散性和金属的还原度 (零价金属百分比 )。研究结果还表明随着金属含量的增加催化活性增大 ,在电催化反应中钴的加入增大了银的催化活性。     

聚苯乙烯邻氨基苯甲酸负载钯催化剂的加氢性能研究

含有双配位基的聚苯乙烯邻氨基苯甲酸与钯络合物反应制得螫合的配位高分子钯催化剂。用甲醇-水(pH=12)还原可得晶粒分布均匀的胶态钯催化剂,它们对烯烃的加氢具有良好的催化作用。研究表明,钯络合物上原有配体的给予性常数(E_n)与负载后络合催化剂的加氢活性具有良好的线性关系,金属粒径为40—50A的催化剂对己烯-1的加氢活性最高。本文还研究了溶剂极性,载体孔结构及底物对催化剂活性的影响。     

固载超强酸催化剂制备及催化合成乙酸正丁酯的研究

研究了把稀土硫酸盐,分别固载于人工沸石、活性炭和强酸型阳离子树脂作为酯化催化剂,从中选出了较好的酯化催化剂－强酸型阳离子树脂固载稀土催化剂,此催化剂用于合成乙酸正丁酯,产率达到97.24%,并对催化剂的催化性能进行了讨论。     

Efficient and Magnetically Recoverable “Click” PEGylated γ‐Fe2O3–Pd Nanoparticle Catalysts for Suzuki–Miyaura,Sonogashira, and Heck Reactions with Positive Dendritic Effects

The engineering of novel catalytic nanomaterials that are highly active for crucial carbon–carbon bond formations, easily recoverable many times, and biocompatible is highly desirable in terms of sustainable and green chemistry. To this end, catalysts comprising dendritic “click” ligands that are immobilized on a magnetic nanoparticle (MNP) core, terminated by triethylene glycol (TEG) groups, and incorporate Pd nanoparticles (PdNPs) have been prepared. These nanomaterials are characterized by transmission electron microscopy (TEM), high‐resolution TEM, inductively coupled plasma analysis, Fourier transform infrared spectroscopy, X‐ray photoelectron spectra and energy‐dispersive X‐ray spectroscopy. They are shown to be highly active, dispersible, and magnetically recoverable many times in Suzuki, Sonogashira, and Heck reactions. In addition, a series of pharmacologically relevant or natural products were successfully synthesized using these magnetic PdNPs as catalyst. For comparison, related PdNP catalysts deposited on MNPs bearing linear “click” PEGylated ligands are also prepared. Strong positive dendritic effects concerning ligand loading, catalyst loading, catalytic activity, and recyclability are observed, that is, the dendritic catalysts are much more efficient than non‐dendritic analogues.     

离子交换树脂在有机催化反应中的应用进展

总结了阳离子交换树脂催化剂和阴离子交换树脂催化剂分别在酯化、烷基化、醚化、缩合、异构化、环氧化等有机合成反应中的应用进展,评述了离子交换树脂催化剂的催化性能和可回收利用性,展望了未来离子交换树脂催化剂的开发和发展方向。     

钯-高分子载体催化剂对糠醛加氢液相反应的研究

以弱碱性苯乙烯系阴离子交换树脂[D392,-NH₂,D382,-NHCH₃,D301R,-NH(CH₃)₂],强碱性苯乙烯系阴离子交换树脂[201×7DVB,-NH⁺(CH₃)₃]和弱碱性环氧系阴离子交换树脂(701,-NH₂)为载体制备了3种钯-高分子载体催化剂.考察了反应条件、高分子载体的种类、钯含量和催化剂用量对糠醛催化加氢生成四氢糠醇反应及催化性能的影响.在体积分数为50%的乙醇-水溶液和水中对糠醛常压液相加氢反应,钯-高分子载体(阴离子交换树脂D392,-NH₂,D382,-NHCH₃)催化剂均可使糠醛的加氢反应转化率达100%,生成四氢糠醇的选择性达98%以上,而用金属钯为催化剂的转化率达70%以上,选择性达97%以上.同时用XPS分析了高分子载体催化剂的结构与催化加氢反应性能的关系.     

胺基化树脂负载Pd(0)对Heck反应催化性能的研究

将氯球用胺化剂、乙二胺、胍进行胺化后负载氯化钯, 在乙醇溶液中用硼氢化钾还原, 制备了含胺功能基树脂负载钯(0)的催化剂; 研究了催化剂对含各种取代基碘代苯与丙烯酸的Heck芳基化反应催化性能. 结果表明, 该类催化剂具有良好的催化活性和重复使用性能, 其中用乙二胺功能化树脂负载的Pd(0)催化剂在90 ℃重复使用17次时能保持良好的催化活性. 催化剂反应前后的SEM形貌图和过滤液的活性试验表明催化剂活性组分Pd(0)在反应中有沥取(leaching)现象.     

固体酸催化二氟二苯甲酮和苯胺缩合合成N-(双(4-氟苯基)亚甲基)苯胺

以固体酸为催化剂,4,4’-二氟二苯甲酮与苯胺脱水缩合,合成了N-(双(4-氟苯基)亚甲基)苯胺.比较了不同固体酸催化剂H型ZSM-5、Na型ZSM-5、介孔分子筛MCM-41(Al)及强酸型离子交换树脂Amberlyst 15的催化效果.使用比表面、NH3-TPD对催化剂进行了表征,并与催化效果关联.考察了催化剂用量、原料摩尔比、浓度及溶剂等反应条件对产物收率的影响.产物通过熔点、核磁共振谱进行了表征.结果表明,HZSM-5固体酸催化剂具有优异的催化作用.在优化条件下,以对二甲苯为反应溶剂和脱水剂,4,4’-二氟二苯甲酮0.1 mol,苯胺0.2 mol,催化剂用量2.0 g,反应24 h,产物收率达91%.此外,催化剂易于分离,能够重复使用多次.     

Microwave-assisted immobilization of β-cyclodextrin on PEGylated Merrifield resins

β-Cyclodextrin was immobilized on PEGylated Merrifield resin through cross-linking with 1,6-hexamethylene diisocyanate (HMDI) reagent, using conventional and microwave-assisted methodologies. FT-IR analysis of the solid intermediates indicated the attachment of the linker arm to the resin due the appearance of characteristic bands centered at 1716 and 2270 cm⁻¹ and the attachment of cyclodextrin to the resin was accompanied with increased absorption at the OH stretching regions (3330-3400 cm⁻¹). β-Cyclodextrin linked PEGylated resins are water insoluble and can be used to trap volatile organic compounds (VOCs) from water and subsequently be analyzed by headspace HS/GC, after simple filtration and drying steps.     

聚偏二氯乙烯负载金鸡纳碱催化剂的合成及其对不对称Michael反应的催化性能

将天然的金鸡纳碱——辛可宁与聚偏二氯乙烯进行接枝反应,制备了聚偏二氯乙烯负载辛可宁的催化剂.将制备的催化剂用于催化不对称Michael反应,并探索了溶剂、催化剂用量、温度、底物等不同条件对其催化性能的影响.结果表明,该催化剂在甲苯中有很高的催化活性和较好的立体选择性,Michael反应中部分产率达到80%以上,e.e值达到72%,且该催化剂具有一定的重复使用性能.     

Effect of the Polymeric Matrix of a Catalyst on Its Activity in Hydrogenation

The swelling degree of ion-exchange resin AB-17-8-OH and palladium-containing catalysts based on this resin were studied. The effects of the diameter of polymeric support grains and temperature on the activity of the catalysts in model reactions of nitrobenzene and -nitronaphthalene hydrogenation were investigated. It was found that the catalyst preparation procedure and the particle size appreciably affect the rates of these reactions.     

新形态全氟磺酸树脂催化剂研究进展

全氟磺酸树脂是绿色固体酸催化剂，对许多反应有较好的催化活性和选择性。但由于全氟磺酸树脂比表面较低，埋没在氟碳基体中的酸性中心不易被反应物所接近，质量比活性低。本文对近年来新形态全氟磺酸树脂，如多孔、负载化、纳米复合物及其改性的全氟磺酸树脂的催化作用进行了综述，文献结果表明全氟磺酸树脂纳米复合物对很多有机合成反应具有很高的催化活性。     

4-氨基吡啶树脂负载钯(Ⅱ)催化Heck反应研究

将4-氨基吡啶树脂负载钯配合物（简写为4-APR-Pd(Ⅱ)）用于卤代或杂环卤代芳烃与烯烃的Heck反应可以获得满意的收率,该法具有环境友好、实用性及树脂催化剂的重复使用性能等特点。并对反应条件进行了讨论,所得产物用1H NMR、13C NMR、红外光谱及元素分析进行了表征。