亲电聚合路线合成聚醚醚酮酮砜的研究

用4,4′-二苯氧基二苯砜(DPODPS)分别与对苯二甲酰氯(TPC)、间苯二甲酰氯(IPC)或2,5-二氯对苯二甲酰氯(DCC)在1,2-二氯乙烷(DCE)中,以无水 AlCl_3为催化剂,在 N-甲基吡咯烷酮(NMP)存在下,通过付-克亲电聚合反应,制得了五种不同结构的聚醚醚酮酮砜(简称PEEKKS)。用红外光谱(IR)、X-射线衍射(XRD)、扫描电镜(SEM)、差示扫描量热(DSC)、热重(TG)及耐溶剂试验,对聚合物进行了表征。结果表明,五种聚合物的对数比浓粘度(η_(inh))均达到0.85以上.具有较低的熔融温度、良好的溶解性能和耐高温性能,PEEKKS 属于非晶态聚合物。     

Benzylation of thiophene using zinc and iron chloride modified montmorillinite clay

Montmorillinite clays, modified with either Zn(II) or Fe(III) chlorides have been used to catalyze the Friedel-Crafts alkylation of thiophene. High yields (ca. 80%) of 2- and 3-benzylthiophene mixtures were obtained using either catalyst in chlorobenzene or nitrobenzene solvent at 80°C. The ratio of 2–3-products was found to be controlled by their relative stability. Reactions were most rapid in nitrobenzene solution (<5 min) and resulted in formation of the 2-isomer as the only mono-substituted product. This is believed to be the first example in which an alkylation of thiophene has been limited to one regio-isomer.     

磷酸二苯酯催化的2-吲哚甲烷胺衍生物的合成

以磷酸二苯酯为催化剂,3-甲基吲哚类化合物与亚胺通过Friedel-Crafts加成反应一步合成了具有广泛药理活性的2-吲哚基甲烷胺类化合物,对反应条件进行优化。结果表明,当n(3-甲基吲哚类)∶n(亚胺)∶n(磷酸二苯酯)=1.0∶2.0∶0.1,其中,磷酸二苯酯0.0025 mmol,1 mL无水二氯甲烷作溶剂,室温下反应0.5 h时,即可得到高收率2-吲哚基甲烷胺类衍生物（85%~90%）。产物经 1HNMR、13CNMR 和 HRMS 进行了结构确定。     

4-氟-2-氯苯胺的合成研究

介绍了以 4 氟苯胺为原料 ,通过乙酰化、氯代、水解三步制备 4 氟 2 氯苯胺的方法 ,对主要的影响因素作了考察并得出结论 :乙酰化反应温度应小于 30℃ ;氯代中 2 /SO2 Cl2为 1∶0 9(mol/mol)时较好 ;在水解阶段盐酸浓度控制在 4mol/L较佳 ,4 氟 2 氯苯胺的纯度大于 99% ,总收率达到 70 %     

4,5-二甲基-1,2-二苯胺的合成工艺改进

以3,4-二甲基苯胺为原料,合成了4,5-二甲基-1,2-二苯胺,产品收率达69%以上。在乙酰化、硝化反应中引入了1,2-二氯乙烷溶剂。用正交实验确定了最佳原料配比:n(3,4-二甲基苯胺)∶n(醋酸酐)∶n(硫酸)=1.00∶1.15∶1.10,硝化反应温度为13°C,反应时间为3.5h,硝化产物收率为90.56%,溶剂回收率95%以上。改进后,每摩尔母体的醋酸酐用量由303g减少至118g,浓硫酸用量由304g减少至108g。     

硝化法制备对氨基间硝基苯磺酸的研究

以对氨基苯磺酸为起始原料 ,经过乙酰化、硝化、水解三步来制备标题物。通过正交试验找出了酰化的最佳反应条件为 :对氨基苯磺酸与乙酐的摩尔比为 1∶1.0 5 ,反应总时间为 1.5h ,反应温度为 2 5℃ ,酰化介质为酰化反应前用碳酸钠及水将对氨基苯磺酸完全溶解 ,使混合液 pH值为 5～ 6 ,反应过程中不再补加碳酸钠 ,其酰化转化率可达 99.6 % ,酰化产物的固体收率可达 96 .0 % ;硝化反应的最佳条件为 :硝化剂用 90 .2 %的硝酸 ,对乙酰氨基苯磺酸与硝化剂的摩尔比为 1∶1.0 5 ,反应温度为 10℃ ,浓硫酸与对乙酰氨基苯磺酸的摩尔比为 8.3∶1,其硝化转化率可达 96 .0 % ,硝化反应的选择性好 ,对氨基邻硝基苯磺酸的量不到 1.0 %。     

取代2-四氢萘酮的一步合成新方法研究

本文介绍了一步法制备取代2-四氢萘酮的新方法,与常规合成方法相比,该法具有明显的优点:不需要先将羧酸转化成酰氯,避免了三氯化铝以及含氯溶剂的应用,并使催化剂得以循环利用。因此,该方法安全、环保,有望取代常规的付-克反应在工业上的应用。     

Reactive compatibilization of PE/PS blends. Effect of copolymer chain length on interfacial adhesion and mechanical behavior

This paper deals with in situ compatibilization of PE/PS blends via Friedel-Crafts reaction, performed at the interphase. Two polyethylenes having different molecular weights, and the same PS, were used along a wide range of catalyst concentration. The influence of the graft copolymer architecture and content on the efficiency of blend compatibilization was studied. The emulsifying effect, morphological aspects and mechanical behavior were also assessed for these blends. The amount of copolymer formed increases with catalyst concentration and the short chain length fraction of the homopolymers. The high molecular weight (MW) copolymers behaved as better compatibilizers as they showed, at the cmc, greater graft copolymer concentration than the low MW ones. A substantial increase in interfacial adhesion and particle size reduction was observed, even at catalyst concentrations as low as 0.3 wt%. In correspondence, mechanical properties, like ductility and yield strength, were enhanced by the effect of this Friedel-Crafts reaction's compatibilization.