基于生物催化法的食品熏蒸剂环氧乙烷制备

为了探索一种反应条件温和、方法简单的食品熏蒸剂环氧乙烷制备方法,采用甲基弯菌IMV 3011(Methylosinus trichosporium IMV 3011)细胞作为生物催化剂,催化乙烯的环氧化反应生成环氧乙烷,确定了反应条件。结果表明:反应器中气相的组成为氧气50%、乙烯20%、氮气30%(体积分数),30℃、150 r/min振荡反应8 h,采用固定化形式催化剂,环氧乙烷生成量为34μmol/mg,利用甲烷培养对其循环再生,再生8次催化剂中甲烷单加氧酶(MMO)活力仍保留89%,环氧乙烷物质的量为3.4 nmol。     

Polymers and polymer building blocks from meadowfoam oil

Meadowfoam oil methyl ester was metathetically cleaved with ethylene catalyzed by Re₂O₇–B₂O₃/Al₂O₃–SiO₂ + SnBu₄ or bis(tricyclohexyl phosphine) benzylidene ruthenium dichloride yielding -olefins, ,ω-dienes and 5-hexenoic acid methyl ester as the main product. The corresponding ω-epoxy fatty acid ester was achieved by chemoenzymatic epoxidation with H₂O₂ in the presents of Novozym^® 435. Glutaric acid mono methyl ester was synthesized by ruthenium-catalyzed oxidative cleavage with peracetic acid. Hydrocarboxylation with carbon monoxide/methanol yielded pimelic acid dimethyl ester. Metathetical dimerization of 5-hexenoic acid methyl ester yielded 5-decen-dioic acid dimethyl ester, which was subsequently polycondensed with ethylene glycole and 1,4-butanediol to high molecular weight polyesters. The ω-unsaturated ester was directly copolymerized with ethylene by an insertion-type palladium-catalyzed reaction to a high molecular weight functional polyolefin. The 5-epoxy hexanoic acid ester was polymerized to a comb like polyether.     

环氧冰片烯的合成与结构表征

冰片烯为原料,m-CPBA作环氧化剂合成了冰片烯的环氧化物,研究表明合成的最佳工艺条件为:m-CPBA作氧化剂,n(冰片烯)∶n(m-CPBA)为1∶3,在20℃条件下反应时间2.0 h,得无色透明晶体,得率53%,纯度91.03%,m.p.71.2～72.4℃。用1H NMR、13C NMR、FT-IR和GC-MS对产物的结构进行了表征,并探讨了冰片烯环氧化反应的机理。     

杂多酸负载介孔分子筛催化α-蒎烯的环氧化反应

以浸渍法将自制的PW（磷钨酸）负载在介孔分子筛上,探讨负载量、催化剂煅烧温度等对催化剂性能的影响,用傅立叶红外光谱对催化剂的结构进行表征,并将该催化剂用于α-蒎烯与低浓度过氧乙酸的环氧化反应。结果表明：α-蒎烯与过氧乙酸的物质的量比为3∶1,相转移催化剂四丁基溴化铵的浓度为0.06 mol/L,PW/MCM-41催化剂的用量为3%（占原料）,在三氯甲烷中反应2.0 h,且维持在15℃以下,α-蒎烯的转化率达75.20%2,、3-环氧蒎烷的选择性为63.79%。     

NaY分子筛负载金属Salen催化剂催化α-蒎烯环氧化

采用普通热溶剂法和微波加热法将SalenMnCl成功负载于NaY分子筛的超笼中,通过FT-IR、XRD、TG和比表面分析方法对催化剂进行了表征。以此负载型催化剂催化低浓度过氧乙酸氧化α-蒎烯制备α-环氧蒎烷,比较了2种方法制备的催化剂性能,然后用响应曲面法探索最佳反应条件,并在该条件下研究负载型催化剂循环使用情况。结果表明,2种方法制备的分子筛负载型SalenMnCl催化剂均可催化α-蒎烯环氧化反应,且催化效果微波法优于普通热溶剂法。微波法制备的SalenMnCl/Y-MW催化剂催化反应的最优条件为:过氧乙酸与α-蒎烯物质的量之比值为1.43,反应温度为10℃,反应时间为3.75 h,在此条件下产物产率达91.60%。同时,该负载型催化剂重复使用5次,产物产率仍达76%以上,其具有较好的稳定性,可循环利用。     

2-(4-氯苯基)-1-(1H-1,2,4-三唑-1-基)-2-丁醇的合成研究

唑醇类杀菌剂对植物的常见致病菌如鞭毛菌、担子菌、半知菌等均有很好的预防和治疗作用,在农药领域应用十分广泛。以对氯苯丙酮为原料,经Corey-Chaykovsky环氧化,再与1H-1,2,4-三氮唑缩合,合成了唑醇化合物2-(4-氯苯基)-1-(1H-1,2,4-三唑-1-基)-2-丁醇。探讨了环氧化反应的关键因素,收率可达97.9%。对缩合反应条件进行了正交优化：以碳酸氢钠为碱催化剂,环氧化物、1H-1,2,4-三氮唑、碳酸氢钠的摩尔比为1.0∶1.5∶2.1,反应温度130℃,反应5 h,缩合收率可稳定在82.0%以上。     

Aldrin epoxidation and dihydroisodrin hydroxylation as probes of in vivo and in vitro oxidative metabolic capability of some caterpillars

Comparative biochemical studies are productive means to study factors that limit both beneficial and harmful effects of chemicals. Reactions such as aldrin epoxidation and dihydroisodrin hydroxylation are valuable assays of oxidative metabolism in scientific studies of chemical biology in insects, subhuman primates and other living things. The tissue distribution of activity in caterpillars may have functional significance. Localization of relatively high concentrations of these cytochrome P450 monooxygenases in gut tissue of lepidoptera may represent an important means to minimize absorption of lipophilic foreign chemicals in food. Some polychlorocycloalkanes permit in vivo and in vitro studies owing to their stability, acceptable toxicity and relatively simple pattern of metabolism. In vivo studies to assess the significance of in vitro findings are feasible with substrates such as aldrin, dihydroisodrin (DHI) and oxidative methylenedioxyphenyl inhibitors such as piperonyl butoxide (PBO) or carbon monoxide. Biphasic dose-dependent decreased and increased DHI-OH formation resulted from PBO pretreatment by gut, fat body, head and Malpighian tubule homogenates of cutworms and gut and fat body (the only tissues tested) of cabbage looper Trichplusia ni (Hübner) and black cutworm Agrotis ipsilon (Hüfnagel). The biphasic in vivo responses of caterpillars to PBO are a reminder of the complexity of biochemical and physiological responses of organisms coexposed to chemicals that are classified, often glibly, as toxic substances and metabolic inhibitors and inducers. Knowledge of dose and time relationships demands very careful evaluation in living things in the environment.     

蓖麻油基含硅阻燃增塑剂的合成及其在聚氯乙烯中的应用

为提高增塑剂的阻燃性能,以可再生资源蓖麻油合成了一种蓖麻油基含硅阻燃增塑剂(Si-ECO),并将其应用到聚氯乙烯(PVC)中。首先将蓖麻油与三甲基氯硅烷反应得到中间体(Si-CO),再与双氧水、甲酸等进行环氧化得到最终产品。采用傅里叶红外光谱(FT-IR)和核磁共振氢谱(~1H NMR)对分子结构进行表征。将该蓖麻油基含硅增塑剂与PVC以及其他助剂进行共混注塑,得到不同含量Si-ECO的PVC树脂。以动态机械分析(DMA)、热重(TG)以及极限氧指数(LOI)等方法测试共混树脂的热力学性能和阻燃性能;以万能力学试验机表征力学性能。试验结果表明:随着Si-ECO阻燃增塑剂含量的增加,其热稳定性有所提高,同时残炭量也增加到4.72%;通过DMA分析可知,该蓖麻油基增塑剂Si-ECO与PVC具有良好的相容性,且能有效提高树脂的阻燃性能,体系的LOI从25.0增加到30.7,热释放速率(HRR)和总释放热(THR)分别为263.14 k W/m^2和29.5 MJ。以蓖麻油为基础合成具有阻燃功能的增塑剂具有广阔的发展前景。     

植物甘油三酸酯油及其衍生物在聚合物领域的应用

综述了天然甘油三酸酯油及其衍生物在聚合物领域的研究与开发动态、重点研究内容、开发途径及应用前景.指出了天然甘油三酸酯油及其衍生物应用于聚合物领域时存在的问题及发展方向.     

固定化甲烷氧化菌细胞催化乙烯环氧化反应动力学研究

以甲基弯菌IMV 3011(Methylosinus trichosporium IMV 3011)为试验对象,活性炭为载体,吸附法制成固定化甲烷氧化菌细胞,催化乙烯环氧化反应,研究内外扩散对环氧化速率影响,通过控制单一变量法,建立该反应幂指数速率方程。结果表明,通过Mears方程验证,可忽略内扩散对环氧化速率影响;当转速高于200 r·min~(-1)时,可忽略外扩散对环氧化速率影响。乙烯环氧化反应幂指数速率方程中,各因素反应级数分别为:乙烯0.6983、氧气0.2715、环氧乙烷-1.0185、催化剂0.5635,通过阿伦尼乌斯方程拟合线得到反应活化能22.575 k J·mol~(-1)。利用幂指数速率方程可计算乙烯环氧化反应环氧化速率,拟合试验表明,测定值与计算值具有良好拟合性。