Propane‐1,2‐diols from Dilactides,Oligolactides, or Poly‐L‐lactic Acid (PLLA): From Plastic Waste to Chiral Bulk Chemicals

The preparation of racemic or enantioenriched propane‐1,2‐diol from dilactides, oligolactides, or poly‐L ‐lactic acid (PLLA) is described. The transformation is carried out as tandem reactions in MeOH, covering hydrolysis and subsequent hydrogenation by using copper chromite as a catalyst. The starting material present undesired side products of the PLLA synthesis or PLLA waste.     

乙酰丙酮氧钼催化的苯乙烯双羟化反应

以钼酸铵与乙酰丙酮反应生成催化剂乙酰丙酮氧钼MoO2(acac)2,考察了反应溶剂、氧化剂存在形式、不同助催化剂、反应温度、底物配比和催化剂量对苯乙烯双羟化反应的影响。在优化的反应条件下,以过氧叔丁醇为氧化剂得到苯乙烯双羟化反应的转化率、化学选择性和分离产率分别为85.2%、70.7%和53.3%。并探讨了可能的催化机理以及改进方向。     

The synthesis and cationic polymerization behavior of ambifunctional monomers

The synthesis of a novel series of ambifunctional monomers containing cationically polymerizable vinyl and 1-propenyl ether or 1-butenyl ether groups in the same molecule has been carried out. Studies of the onium salt-induced photopolymerizations of these monomers indicate that both functional groups are highly reactive and that they undergo extensive copolymerization. © 1996 John Wiley & Sons, Inc.     

水溶液中锌粉促进邻二醇合成的研究

邻二醇是有机合成中重要的合成子,是合成烯烃、酮类化合物的重要中间体,广泛用于农药、医药等精细化工品的合成.合成邻二醇最有效的方法是羰基化合物的还原偶联,通常由羰基化合物与相应的金属试剂或金属络合物作用而实现,往往反应时间长,要求的条件苛刻,有的收率比较低.     

高效凝胶过滤色谱填料KH-s-GFC300的合成与评价

以碱溶法制备的高孔隙度硅胶为基质,与γ-环氧丙基丙氧基三甲氧基硅烷配基进行共价键合,经过酸性水解,使其转化为二醇基,制成了高效亲水凝胶色谱填料。键合反应中采用70 ℃回流冷凝管,使生成的甲醇可顺利地排到体系外,促使反应向有利于键合的方向进行,以获得较高的配基密度。研究表明,水解反应条件与配基密度以及柱效密切相关。当配基密度为2.6~3.5 μmol/m2时,才能显示出较高的柱效。蛋白质分离实验结果显示,此填料的相对分子质量排阻极限为300000,牛血清白蛋白的回收率为99％。     

顶空气相色谱法测定烟用胶中残余单体

采用顶空气相色谱(HS-GC)法对卷烟用胶中甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和乙酸乙烯酯7种残余单体进行了分析。方法采用DB-VRX石英弹性毛细管色谱柱分离,氢火焰离子化检测器检测。7种单体能够完全分离,线性良好,线性相关系数在0.9985～0.9992之间,检测限在0.0030～0.0039mg/mL范围,相对标准偏差(RSD)小于1.92%。该方法操作简便、快速、高效、准确、灵敏度高,实用性强,可用于胶粘剂中残余单体的测定。     

IRMOF-1衍生介孔ZnO微球催化合成低聚聚碳酸酯二醇

IRMOF-1是一种最经典的IRMOF系列材料,通过直接在空气中不同温度下热处理IRMOF-1得到三种ZnO催化剂,并采用XRD、SEM、BET、CO_2-TPD等分析技术对所得样品的晶体结构、表观形貌、孔结构、表面碱性进行了表征。结果显示,ZnO为球状结构,是一种典型的介孔材料,BET比表面积和孔径分别为49.7~62.2 m2/g和2.18~2.92 nm。研究了ZnO微球在碳酸二苯酯(DPC)与新戊二醇(NPG)酯交换合成低聚碳酸酯二醇(PCDL)反应中的催化性能。结果表明,500℃下得到的ZnO微球在DPC与NPG酯交换反应中表现出良好的催化活性。     

过渡金属催化的醇类脱氧脱水反应

开发和利用环境保护型的可再生新能源是缓和与解决能源环境问题的重要举措.生物质可作为燃料和可再生平台化学品的来源.高含氧量与过度官能化的生物质原料不能直接使用,因此降低生物质原料的含氧量并将其转化为燃料与增值化学品的方法是实现生物质能广泛应用的关键.还原脱氧的方法主要有热解、水解、氢解、脱羧/脱羰反应、加氢脱氧与脱氧脱水反应等.本综述详细介绍了铼、钼、钒、钌等四种过渡金属催化的由二元醇及多元醇制备相应烯烃的脱氧脱水反应,主要从均相催化、还原剂使用、机理研究和非均相催化等方面做了多角度的总结.铼催化的脱氧脱水反应具有选择性好和烯烃产率高等优点,钼、钒、钌等金属是可能替代昂贵的铼金属的催化剂.     

Bis(β‐ketoamino)copper(II)/methylaluminoxane systems for homo‐ and copolymerizations of methyl acrylate and 1‐hexene

Two bis(β‐ketoamino)copper [ArNC(CH₃)CHC(CH₃)O]₂Cu ( 1 , Ar = 2,6‐dimethylphenyl; 2 , Ar = 2,6‐diisopropylphenyl) complexes were synthesized and characterized. Homo‐ and copolymerizations of methyl acrylate (MA) and 1‐hexene with bis(β‐ketoamino)copper(II) complexes activated with methylaluminoxane (MAO) were investigated in detail. MA was polymerized in high conversion (>72%) to produce the syndio‐rich atactic poly(methyl acrylate), but 1‐hexene was not polymerized with copper complexes/MAO. Copolymerizations of MA and 1‐hexene with 1 , 2 /MAO produced acrylate‐enriched copolymers (MA > 80%) with isolated hexenes in the backbone. The calculation of reactivity ratios showed that r(MA) is 8.47 and r(hexene) is near to 0 determined by a Fineman‐Ross method. The polymerization mechanism was discussed, and an insertion‐triggered radical mechanism was also proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1113–1121, 2010     

Investigation of the solid phase synthesis of tyrosine‐derived diphenol monomers with resin‐bound carbodiimide coupling reagents

Tyrosine‐derived pseudo‐polypeptides have recently been established as potential biomaterials. The bulk production of these polymers is dependant upon the convenient synthesis of tyrosine‐derived diphenolic monomers. Suitable solution phase methods for the synthesis of such monomers, with transient activated esters, have been reported previously by Kohn, J.; Langer, R. In Biomaterials Science: An Introduction to Materials in Medicine; Ratner, B. D.; Hoffman, A. S.; Schoen, F. J.; Lemons, J. E., Eds.; Academic Press: New York, 1996; pp 64–72. However, for all the methods reported by them, purification and isolation of the diphenol monomer involves rigorous extraction, column purification, or an extensive aqueous workup. These may lead to the incorporation of solvent‐based as well as inorganic impurities and also may lead to difficulties in the process scale‐up. In this article, an alternate and relatively more convenient method for the synthesis of tyrosine‐based diphenol monomers is reported. This involved the investigation of polymer resin‐bound carbodiimide in the solid‐phase synthesis of L‐tyrosine‐based diphenolic monomers. This method was found to eliminate the need for rigorous purification processes and was found to maintain reasonable yield as well as maintain purity of the final monomer product. The monomer was able to produce polymers of a reasonably high‐molecular‐weight and a narrow polydispersity. The amide bond formation by such a polymer‐tethered reagent can be described to follow a reverse‐Merrifield sense and the method is relatively convenient to scale up. The L‐tyrosine‐based diphenolic monomeric compound formed by this method was analyzed by NMR, Fourier transform infrared, and elemental microanalysis techniques for chemical structure and composition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4906–4915, 2004