【作者】 李静；

【导师】 单永奎；

【作者基本信息】 华东师范大学 ， 无机化学， 2004， 硕士

【摘要】 α-甲基苯乙烯（AMS）在工业上是异丙苯法联产苯酚和丙酮时所产生的一种副产物，而异丙苯法生产苯酚和丙酮是目前国内生产的主流工艺。年产万吨苯酚和丙酮的装置约副产500吨AMS。目前，国内对AMS的综合利用处于比较单一状态，主要仍是将其催化加氢还原生成异丙苯，仅有小部分用来合成二聚体或用于丙烯腈-丁二烯-苯乙烯共聚物（ABS）中作为添加剂。因此，综合开发利用AMS的工艺技术是合理利用资源，促进化学工业持续发展的重要措施，对于经济发展和环境保护均有重要意义。 AMS二聚产物有多种用途。AMS线性二聚物2，4-二苯基-4-甲基-1-戊烯在高分子合成及加工、润滑油改性、颜料和涂料的制造等方面应用广泛。AMS环状二聚物1，1，3-三甲基-3-苯基茚满是一种具有广泛用途的茚满类有机化合物，其热稳定性和抗氧化性能均好，并与许多高分子材料有良好的相容性，可用作塑料和橡胶的增塑剂，并可改善高分子材料的阻燃性。 本论文选用季胺盐型离子液体盐酸三乙胺-三氯化铝（Et₃NHCl-AlCl₃）和盐酸三乙胺-三氯化铁（Et₃NHCl-FeCl₃）为催化剂，研究了在离子液体催化下的AMS二聚反应。首次发现离子液体Et₃NHCl-AlCl₃是AMS环二聚反应的优良催化剂，反应在无溶剂下进行，反应体系自身的放热可以提供反应的热量来源，反应时间短，五分钟内反应物AMS的转化率达到100％，环二聚体的选择性高，催化剂经离心与产物分离，不存在复杂的后处理步骤。在用Et₃NHCl-FeCl₃作催化剂时，根据所加入溶剂的极性不同，可得到高选择性的线二聚体或环二聚体，线性二聚体2，4-二-苯基-4-甲基-1-戊烯的选择性最高可达100％。 此外，本论文还选用SBA-15负载PW（PW／SBA-15），为AMS二聚反应催化剂。结果显示PW／SBA-15是AMS环二聚反应的优良高效催化剂，原料AMS转化率达到100％，环二聚体选择性高达100％，优于前人的报道，体现了100％原子经济反应的优越性，且反应时间短，催化剂重复使用效果好，反应过程清洁无污染，可以说PW／SBA-15是AMS环二聚反应的绿色催化剂，有很好的工业化前景。更多还原

【Abstract】 α-methylstyrene(AMS) is the byproduct of industrial process producing phenol and acetone. This process is the main way to yield phenol and acetone in our country. With the increasing output of AMS, how to utilize AMS is becoming an urgent problem. The dimerization of AMS is a promising research field and much attention has been paid to this domain in last decade.The dimers of AMS have been applied in chemical industry widely. The linear dimers are used as the controlling agents of molecular weight in the production of copolyrriers, such as styrene-butadiene rubber(SBR). The linear dimer 2,4-diphenyl-4-methyl-l-pentene is also an alternative for dodecylmercaptane. Adding cyclic dimer into polyethene(PE) can increase flowability, improve processability and decrease melt viscosity, processing temperature of PE plastics. The hydrogenated forms of AMS dimers are of industrial value as component in lubrication compositions.The research work is focused on the dimerization of AMS catalyzed by ionic liquids Et3NHCl-AlCl3 and Et3NHCl-FeCl3. We find that Et3NHCl-AlCl3 possesses very good performance of catalysis for the cyclic dimerization of AMS. The reaction of the dimerization of AMS is carried out without the presence of solvent for five minutes, AMS converts to products totally, and the selectivity of cyclic dimer is very high(>90%). When using Et3NHCl-FeCl3 as the catalyst, we can get the cyclic dimer or linear dimers by adding solvent with different polarity.In this paper, we also select SBA-15 supported PW (PW/ SBA-15) as catalyst of the dinierization of AMS. The results indicate that PW/ SBA-15 is a good catalyst of this reaction. The conversion of AMS and the selectivity of cyclic dimer reach 100% in the experimental conditions. This process embodies 100% atom economy, and no pollutant releases during the reaction. The results indicate that PW/ SBA-15 is a green catalyst of AMS dimerization.更多还原