摘要
以交联聚苯乙烯(CPS)微球为载体,通过Friedel?Crafts酰基化反应和亲核取代反应化学固载2,2,6,6-四甲基哌啶氮氧自由基(TEMPO),制备了非均相催化剂微球TEMPO/CPS,对其化学结构和形貌进行了表征;考察了主要因素对氯丁酰氯(CBC)与CPS微球Friedel?Crafts酰基化反应的影响,优化了反应条件;将微球与Fe(NO3)3构成共催化剂,用于肉桂醇和1-苯乙醇的分子氧催化氧化.结果表明,CBC与CPS微球的Friedel?Crafts酰基化反应最适宜的Lewis酸催化剂为Al Cl3,最适宜的溶剂为氯仿,反应过程中发生附加交联反应,影响微球强度,适宜的反应温度为75℃,时间为5 h,该条件下制备了TEMPO固载量为1.78 mmol/g的TEMPO/CPS微球.其与助催化剂Fe(NO3)3构成的共催化剂具有高催化活性,可在75℃、常压氧气条件下反应24 h将1-苯乙醇氧化为苯乙酮,1-苯乙醇转化率为88%,也能有效将肉桂醇氧化为肉桂醛.
The immobilization of 2,2,6,6-tetramethyl piperidine nitroxide （TEMPO） on cross-linked polystyrene （CPS） microspheres was realized via Friedel-Crafts acylation reaction and nucleophilic substitution reaction, and the heterogeneous catalyst microspheres TEMPO/CPS were obtained successfully. The chemical structure and morphology of TEMPO/CPS microspheres were characterized. The effects of different factors on the Friedel-Crafts acylation reaction between ehlorobutyryl chloride （CBC） and CPS microspheres were examined, and the reaction conditions were optimized. Finally, a co-catalyst system was constructed by TEMPO/CPS and Fe（NO3）3, which was used in the oxidation reaction processes of cinnamyl alcohol as a primary alcohol and 1-phenethyl alcohol as a secondary alcohol with molecular oxygen as oxidant, respectively. The results show that for the Friedel-Crafts acylation reaction between CBC and CPS microspheres, the optimum Lewis acid catalyst is AlCl3, and the suitable solvent chloroform. During the reaction process, the additional cross-linking reaction occurs, which will weaken the strength of the microspheres. The Friedel-Crafts acylation reaction should be carried out at 75 ℃ and the reaction time should be 5 h. The co-catalyst system of TEMPO/CPS and Fe（NO3）3 possesses high catalytic activity, and under the conditions of lower temperature and ordinary pressure of oxygen, it can make 1-phenethyl alcohol highly effectively transform into acetophenone （1-phenethyl alcohol conversion rate of 88% at 75 ℃ for 24 h） and cinnamyl alcohol into cinnamic aldehyde.
出处
《过程工程学报》
CAS
CSCD
北大核心
2015年第4期677-682,共6页
The Chinese Journal of Process Engineering
基金
山西省自然科学基金资助项目(编号:2013021009-1)
关键词
交联聚苯乙烯
固载
醇
氧化
分子氧
催化
cross-linked polystyrene
immobilization
alcohol
oxidation
molecular oxygen
catalysis
