吡咯亚胺钒络合物催化制备含功能性乙氧基硅烷聚乙烯

发布时间：2018-06-18 22:48

本文选题：聚乙烯 + 有机硅　；参考：《化工学报》2017年02期

【摘要】：通过二甲基乙氧基硅烷与1,7-辛二烯的硅氢加成反应,制备出一种含功能性基团的极性单体——7-辛烯基乙氧基二甲基硅烷(OEMS),在吡咯亚胺钒络合物(VCIP)的催化作用下,该单体可与乙烯配位共聚制备含功能性乙氧基硅烷的乙烯共聚物(PE-co-OEMS)。通过高温核磁共振氢谱及碳谱(1H NMR和13C NMR)、高温凝胶渗透色谱(HT-GPC)和热分析(DSC)等测试方法对共聚物的结构和热性能进行了表征。结果显示,当共单体OEMS的投料量增大至60 mmol·L-1时,共聚反应活性仍可保持在1.2 kg·mmol-1·h-1,OEMS单体插入率为1.3%(摩尔分数);此外,OEMS投料量对于共聚物的分子量(Mw)和分子量分布(PDI)均具有较大的影响,当OEMS投料量为30 mmol·L-1时,共聚物Mw为16900,PDI为2.1;若继续增大共单体的投料量,共聚物分子量增大且分子量分布变宽。熔点(Tm)和结晶焓(ΔHc)随着OEMS插入率的增大而降低。在三氟甲磺酸作用下,PE-co-OEMS交联后凝胶含量接近100%。
[Abstract]:A polar monomer, 7-octenyl ethoxydimethylsilane, was prepared by the hydrosilylation reaction of dimethyl ethoxy silane with 1-octadiene, which was catalyzed by the vanadium complex of pyrroleimide (VCIPs), and a novel polar monomer, 7-octenyl ethoxydimethylsilane, was prepared. The monomer can be copolymerized with ethylene to prepare ethylene copolymer containing functional ethoxysilane (PE-co-OEMS). The structure and thermal properties of the copolymers were characterized by high temperature nuclear magnetic resonance (NMR), 1H NMR and 13C NMR spectra, high temperature gel permeation chromatography (HT-GPC) and thermal analysis (DSCC). The results showed that when the feed amount of co-monomer increased to 60 mmol L-1, The copolymerization activity can still be maintained at 1.2 kg mmol-1 h-1OEMS monomer insertion rate of 1.3 (mole fraction); in addition, the amount of mmol-1 feed has a great influence on the molecular weight of the copolymers and the molecular weight distribution of the copolymers. When the dosages of the copolymers are 30 mmol L ~ (-1), the amount of the copolymers is 30 mmol L ~ (-1). The molecular weight of the copolymers increased and the molecular weight distribution became wider if the feed amount of the copolymers was increased. The melting point Tm) and the enthalpy of crystallization (螖 Hc) decreased with the increase of the insertion rate of OEMS. The gel content of PE-co-OEMS was close to 100 under the action of trifluoromethyl sulfonic acid.
【作者单位】：化学工程联合国家重点实验室浙江大学化学工程与生物工程学院;
【基金】：国家自然科学基金重大国际(地区)合作研究项目(21420102008)~~
【分类号】：TQ317;O643.32

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