AlCl3/促进剂协同催化1-癸烯齐聚制备聚α-烯烃合成油

Preparation of poly-α-olefin synthetic oil through 1-decene oligomerization catalyzed by aluminium chloride promoted by metal chloride

以三氯化铝为催化剂、过渡金属氯化物MCl3(VCl3、CrCl3和TiCl3)为促进剂,催化1-癸烯齐聚制备了具有高黏度指数的聚α-烯烃(PAO)合成油,系统研究了促进剂的作用机制和齐聚反应条件对齐聚反应活性和PAO性能和结构的影响。结果表明:VCl3和CrCl3的加入能明显增加1-癸烯齐聚反应收率和齐聚物的黏度指数。过渡金属氯化物通过双氯桥结构与三氯化铝形成双金属化合物,通过双金属间的协同效应,改变三氯化铝的吸电子能力来增加其催化活性。通过核磁氢谱(^1H NMR)和核磁碳谱(^13C NMR)分析,确定了AlCl3/MCl3催化1-癸烯齐聚遵循阳离子聚合机制,1-癸烯齐聚物中主要的不饱和双键为三取代和双取代内烯烃。过渡金属氯化物促进剂可以调整优势反应途径从而改变齐聚产物的分布。

The poly-α-olefin synthetic oils with high viscosity index were prepared through 1-decene oligomerization catalyzed by the aluminum trichloride catalyst that was promoted by transition metal chlorides(VCl3,CrCl3 and TiCl3).The promotion effect of metal chlorides and the influence of reaction conditions on the oligomerization activity and the properties and structure of the oligomers formed were investigated.The results showed that addition of VCl3 and CrCl3 into AlCl3 catalyst could obviously increase the oligomerization yield and the viscosity index of the oligomers formed.The transition metal chloride enhanced the activation of AlCl3 through forming bimetallic species containing two Al-Cl-V bridging bonds,which presented synergistic effect to increase the electron-withdrawing ability of AlCl3 to improve the activity.The characterization of the oligomers structure by 1H NMR and 13C NMR spectra indicated that 1-decene oligomerization on AlCl3/MCl3 catalyst followed the cationic polymerization mechanism.The main oligomers formed were internal olefins with trisubstituted and disubstituted vinylenes.The transition metal chloride promoters adjusted the distribution of the unsaturated bonds through changing the pathway of the preponderant reaction.