CIESC Journal ›› 2017, Vol. 68 ›› Issue (2): 774-780.DOI: 10.11949/j.issn.0438-1157.20160906

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Preparation of functional ethoxysilane-containing polyethylene through ethylene coordination copolymerization catalyzed by iminopyrrolide vanadium complex

LIU Zhiying, FAN Hong   

  1. State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2016-07-04 Revised:2016-10-25 Online:2017-02-05 Published:2017-02-05
  • Supported by:

    supported by the Major International (regional) Joint Research Project of the National Natural Science Foundation of China (21420102008).

吡咯亚胺钒络合物催化制备含功能性乙氧基硅烷聚乙烯

刘智颖, 范宏   

  1. 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, 浙江 杭州 310027
  • 通讯作者: 范宏
  • 基金资助:

    国家自然科学基金重大国际(地区)合作研究项目(21420102008)。

Abstract:

A well-defined silane-functionalized comonomer, 7-octenylethoxydimethylsilane (OEMS), was synthesized through hydrosilylation reaction of dimethylethoxysilane with 1,7-octadiene. Catalyzed by a vanadium complex bearing iminopyrrolide ligands (VCIP), the functional ethoxysilane-containing polyethylenes (PE-co-OEMS) were synthesized by copolymerization of ethylene with OEMS. The structure and properties of PE-co-OEMSs were characterized with 1H NMR, 13C NMR, HT-GPC and DSC. It was found that catalytic activity still remained 1.2 kg·mmol-1·h-1 when OEMS feeding reached to 60 mmol·L-1, and the OEMS incorporating in the copolymer was 1.3%(mol). Besides, the OEMS feeding had a great influence on the average molecular weight (Mw) and distribution (PDI) of copolymers. The Mw and PDI of PE-co-OEMS were 16900 and 2.1 when OEMS feeding was 30 mmol·L-1. With further increasing the OEMS feeding, Mw increased and PDI became wider. The melting temperature (Tm) and crystallization enthalpy (ΔHc) decreased with the increase of OEMS incorporation. The ethoxysilane-containing copolymers were easily crosslinked under the catalysis of trifluoromethanesulfonic acid, and the copolymer gel contents after crosslinking were nearly 100%.

Key words: polyethylene, silicone, crosslinking, polymer, preparation, synthesis

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%。

关键词: 聚乙烯, 有机硅, 交联, 聚合物, 制备, 合成

CLC Number: