有机化学 ›› 2023, Vol. 43 ›› Issue (10): 3590-3597.DOI: 10.6023/cjoc202305019 上一篇    下一篇

所属专题: 有机硅化学专辑-2023

研究论文

硅宾/有机铝的Lewis酸碱对体系及其丙烯酸酯聚合的引发性能

赵怡玲, 陈志康, 李磊, 刘聪磊, 朱红平*()   

  1. 厦门大学化学化工学院 固体表面物理化学国家重点实验室 福建厦门 361005
  • 收稿日期:2023-05-15 修回日期:2023-08-05 发布日期:2023-09-08
  • 基金资助:
    国家自然科学基金(21972112)

Silylene/Organoaluminum Lewis Pair System and the Initiation Property for Polymerization of (Meth)acrylates

Yiling Zhao, Zhikang Chen, Lei Li, Conglei Liu, Hongping Zhu()   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005
  • Received:2023-05-15 Revised:2023-08-05 Published:2023-09-08
  • Contact: *E-mail: hpzhu@xmu.edu.cn
  • Supported by:
    National Natural Science Foundation of China(21972112)

研究了硅宾/有机铝组成的Lewis酸碱对(LP)体系引发丙烯酸酯类单体聚合的性能, 合成了4种硅宾: L(Ph2P)Si (Si-1, L=PhC(NtBu)2)、L[4-MeC6H4(Ph2P)N]Si (Si-2)、L[2,6-iPr2C6H3(1,5-C8H14B)N]Si (Si-3)、L(LSi)Si (Si-4)和6种有机铝: Al(C6F5)3、AlMe(BHT)2、AliBu(BHT)2、AliBu2(BHT)、AliBu(BHT*)2、AliBu2(BHT*) (BHT=2,6-tBu2-4-MeC6H2O, BHT*=2,4,6-tBu3C6H2O). Si-1/有机铝和Si-4/有机铝LP体系均能引发甲基丙烯酸甲酯(MMA)完全聚合, 活性转换频率(TOF)值为50~400 h-1, 产出PMMA的分子量Mn 82000~271000和分子量分布Đ 1.11~1.81. Si-2/有机铝和Si-3/有机铝LP体系没有活性. Si-1/Al(C6F5)3体系对丙烯酸正丁酯(nBA)、丙烯酸-2-乙基己基酯(EHA)的活性较差, 但是Si-1/其它有机铝都能高效引发nBA和EHA完全聚合. 对nBA, TOF值4.8×104~14.4×104 h-1, 产出PnBA的Mn 100000~179000和Đ 1.08~1.59; 对EHA, TOF值至14.4×104~36.0×104 h-1, 生成PEHA的Mn 81000~240000以及Đ 1.12~1.95. 研究了聚合反应的可能机理.

关键词: 硅宾Lewis碱, 有机铝Lewis酸, Lewis酸碱对聚合引发体系, 丙烯酸酯类单体, 聚丙烯酸酯

The initiation polymerization property of (meth)acrylates by using the silylene/organoaluminum Lewis pair (LP) system is studied. Four silylenes L(Ph2P)Si (Si-1, L=PhC(NtBu)2), L[4-MeC6H4(Ph2P)N]Si (Si-2), L[2,6-iPr2C6H3(1,5- C8H14B)N]Si (Si-3), and L(LSi)Si (Si-4) as the Lewis base (LB) were synthesized, together with six organoaluminums Al(C6F5)3, AlMe(BHT)2, AliBu(BHT)2, AliBu2(BHT), AliBu(BHT*)2, and AliBu2(BHT*) (BHT=2,6-tBu2-4-MeC6H2O and BHT*=2,4,6-tBu3C6H2O) as the Lewis acid (LA). Si-1/organoaluminum and Si-4/organoaluminum LP systems all enable to initiate the complete methacrylate (MMA) polymerization, achieving turnover of frequency (TOF) activities in the range of 50~400 h-1 with PMMA Mn of 82000~271000 and Đ of 1.11~1.81. Neither Si-2/organoaluminum or Si-3/organoaluminum was active. The Si-1/Al(C6F5)3 displayed poor reactivity on n-butyl acrylate (nBA) and 2-ethylhexyl acrylate (EHA). However, the Si-1/other organoaluminums exhibited both complete nBA and EHA polymerizations. For nBA, the TOFs were obtained by 4.8×104~14.4×104 h-1, in which the PnBAs were produced with Mn 100000~179000 and Đ 1.08~1.59. For EHA, the TOFs were up to 14.4×104~36.0×104 h-1, where the PEHAs were yielded with Mn 81000~240000 and Đ 1.12~1.95. The probable polymerization mechanism with the silylene/organoaluminum LP system is investigated.

Key words: silylene as the Lewis base, organoaluminum as the Lewis acid, Lewis pair polymerization, (meth)acrylate monomer, poly(meth)acrylates