不对称硅烷基PNP单活性中心铬催化剂的合成与表征
Synthesis and characterization of unsymmetric silylated PNP single-active central chromium catalyst
陈佩丽 1宋达 2李杨 3郭丽君 3苏秋成 1李翠勤3
作者信息
- 1. 中国科学院广州能源研究所,广东广州 510640
- 2. 中国科学院广州能源研究所,广东广州 510640;中国科学技术大学,安徽合肥 230026
- 3. 东北石油大学化学化工学院聚烯烃新材料省重点实验室,黑龙江大庆 163318
- 折叠
摘要
以γ-氨丙基三乙氧基硅烷和氯代二苯基膦为原料,通过酰化反应合成一种不对称硅烷基PNP配体.条件优化实验确定该硅烷基PNP配体的较佳合成条件为:二氯甲烷为溶剂,三乙胺为缚酸剂,氯代二苯基膦和γ-氨丙基三乙氧基硅烷的物质的量比为2.1∶1.0,氯代二苯基膦的滴加温度为-5 ℃,滴加时间为30 min,反应温度为25 ℃,反应时间为12 h.此条件下,不对称硅烷基PNP配体的收率为91.20％.基于灰色关联分析得出滴加温度是影响不对称硅烷基PNP配体收率的最主要因素.采用合成的不对称硅烷基PNP配体和四氢呋喃三氯化铬为原料,通过络合反应合成不对称硅烷基PNP单活性中心铬催化剂,收率为95.25％.元素分析、FTIR、1H NMR和MS证实合成的硅烷基PNP配体及其相应的铬催化剂的结构与其理论结构相符.该硅烷基PNP单活性中心铬催化剂具有良好的催化乙烯齐聚活性,齐聚产物中C8烯烃含量为72.40％,其性能优于分子间络合的硅烷基Schiff碱亚胺铬催化剂.
Abstract
A silylated PNP ligand with asymmetric structure was synthesized using(γ-aminopropyl)trie-thoxysilane and chlorodiphenyl phosphine as raw materials.The optimal synthetic conditions of the PNP ligand were obtained by conditional experiments and were as follows:dichloromethane was solvent,trieth-ylamine was acid acceptor,the mole ratio of chlorodiphenylphosphine and(y-aminopropyl)triethoxysilane was 2.1∶1,the dropping temperature of chlorodiphenylphosphine was-5 ℃,the dropping time was 30 min,the reaction temperature was 25 ℃ and the reaction time was 12 h.Under the conditions,the yield of the silylated PNP ligand was 91.20％.Based on grey correlation analysis,the dropping temperature was the main factor for the yield of the silylated PNP ligand.The single-active central chromium catalyst based on the silylated PNP ligand was synthesized by complexation reaction with the silylated PNP ligand and chromium chloride tetrahydrofuran complex as materials,and the yield was 95.25％.The chemical struc-tures of the silylated PNP ligand and the corresponding chromium catalyst were confirmed by elemental a-nalysis,FT-IR,1 H NMR,MS and ICP.The single-active central chromium catalyst based on the silylated PNP ligand had good catalytic activity for ethylene oligomerization,and the content of C8 olefin was 72.40％,which was superior to Si-Schiff-Cr based on intermolecular coordination.
关键词
不对称硅烷基PNP配体/灰色关联/铬催化剂/乙烯齐聚Key words
unsymmetric silylated PNP ligand/grey association/chromium catalyst/ethylene oligomeriza-tion引用本文复制引用
基金项目
Key Research and Development Project of Heilongjiang Province(JD22A026)
出版年
2024
NETL
NSTL
万方数据