摘要
以异辛醇改性三氯氧钒(VOCl_3·3(2-ethyl-hexanol))为催化剂前体,倍半乙基铝(EASC)为助催化剂,三氯乙酸乙酯(ETCA)为活化剂进行乙烯/丙烯共聚合,并与传统VOCl_3体系进行对比。考察了EASC和ETCA用量、反应温度对聚合的影响。随EASC用量的增加,2种催化体系活性均先增加后下降,VOCl_3·3(2-ethyl-hexanol)和VOCl_3体系分别在[Al]/[V]比为40和30时达到最高催化活性6. 15 kg EPR/g V·h和4. 97 kg EPR/g V·h。2种催化体系活性均随聚合温度的升高呈下降的趋势,VOCl_3·3(2-ethyl-hexanol)体系的下降幅度低于VOCl_3体系,表明异辛醇有效地稳定了生成的活性中心。差示扫描量热分析和核磁共振碳谱分析表明以VOCl_3·3(2-ethyl-hexanol)体系所合成的共聚物较VOCl_3体系有更高的丙烯插入率和更为无规的结构。
2-Ethylhexanol modified vanadium oxytrichloride [VOCl3·3 (2-ethyl-hexanol)] as catalyst precursor was examined for ethylene/propylene copolymerization with ethylaluminium sesquichloride (EASC) as cocatalyst and ethyl trichloroacetate (ETCA) as reactivator, along with the traditional VOCl3-based system for comparison. The influences of EASC and ETCA loading levels as well as reaction temperature on the polymerization were investigated. With increasing the EASC dosage, the activities of both the systems increase and then decrease. The highest activities of VOCl3·3(2-ethyl-hexanol) and VOCl3-based systems, 6. 15 kg EPR/gV·h and 4. 97kg EPR /gV·h, are observed at [Al]/[V] ratio of 40 and 30 ,respectively. While the catalytic activity of both systems decreases by increasing the polymerization temperature , the decline rate in the VOCl3·3 (2-ethyl-hexanol) system is much lower than that in the VOCl3 system. These results indicate that the presence of 2-ethyl-hexanol effectively stablizes the generated acive species. Determined by DSC and 13C-NMR,the ethylene-propylene copolymer obtained with VOCl3 · 3(2-ethyl-hexanol) system has a higher propylene incorporation and more random structures than that prepared with the VOCl3 system.
作者
那丽华
张璐
惠林海
张春雨
胡雁鸣
张学全
Lihua Na;Lu Zhang;Linhai Hui;Chunyu Zhang;Yanming Hu;Xuequan Zhang(Key Laboratory of Synthetic Rubber,Changchun Institute of Applied Chemistry , Chinese Academy of Sciences,Changchun 130022,China;Shandong Non-Metallic Materials Institute, Jinan 250031 , China)
出处
《高分子材料科学与工程》
EI
CAS
CSCD
北大核心
2019年第1期31-34,40,共5页
Polymer Materials Science & Engineering
基金
国家重点研发计划项目(2017YFB0307100(2017YFB0307103))
关键词
乙烯-丙烯共聚物
钒催化剂
共聚合
ethylene-propylene copolymer
vanadium-based catalyst
copolymerization
