Article
  • Spectroscopic Analysis on the Michael Addition Reaction between Secondary Amino Group Containing Silica Nanoparticles with (Meth)acrylate Monomers
  • Jeon HN, Ha K
  • 2차 아미노기를 갖는 실리카 나노입자와 (메타)아크릴레이트 단량체와의 마이클 부가반응에 대한 분광학적 분석
  • 전하나, 하기룡
Abstract
In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to introduce secondary amino groups on the silica surface. After modification of silica, we investigated effects of different types of (meth)acrylate group containing monomers on the Michael addition reaction to introduce reactive (meth)acrylate groups on the BTMA modified silica surface. We used two kinds of (meth)acrylate monomers, trimethylolpropane ethoxylate triacrylate (TMPET) which has three identical acrylate groups, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) which has one acrylate and one methacrylate group. We used fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand reactions between NH groups on the silica surface with (meth)acrylate groups of TMPET and AHM monomers. We found almost complete Michael addition reaction between all three acrylate groups of TMPET with NH groups on the BTMA modified silica. But, for the AHM treatment of BTMA modified silica, we found Michael addition reaction occurred only between acrylate groups of AHM and NH groups of silica surface, not between methacrylate groups of AHM and NH groups of BTMA modified silica surface.

본 연구에서는 실리카 나노입자를 bis[3-(trimethoxysilyl)propyl]amine(BTMA) 실란 커플링제로 표면 개질한 후, 실리카에 도입되는 2차 아미노기인 -NH기와 Michael 부가반응이 가능한 acrylate기를 가지는 trimethylolpropane ethoxylate triacrylate(TMPET)와 3-(acryloyloxy)-2-hydroxypropyl methacrylate(AHM)로 표면 처리를 하여 반응성(meth)acrylate기를 가지는 brush를 도입하는 연구를 수행하였다. 1분자에 Michael 부가반응성이 있는 acrylate기를 3개 갖는 TMPET와 1분자에 반응성이 있는 acrylate기와 반응성이 없는 methacrylate기를 각각 1개씩 갖는 AHM을 사용하여, 처리 몰(mol)수의 변화가 실리카 표면에 도입되는 (meth)acrylate기에 미치는 영향을 Fourier transform infrared spectroscopy(FTIR), elemental analysis(EA) 및 고체 상태 cross-polarization magic angle spinning(CP/MAS) nuclear magnetic resonance spectroscopy(NMR)법을 사용하여 분석하였다. BTMA로 개질된 실리카를 TMPET로 처리하면, 액체상태의 순수 TMPET와 순수 BTMA의 반응과는 달리 TMPET 1분자당 3개씩 결합있는 acrylate기 대부분이 BTMA의 -NH기와 Michael 부가반응이 일어나는 것을 확인하였다. 따라서 BTMA로 처리한 실리카에 Michael 부가반응으로 반응성 (meth)acrylate기를 도입하기 위하여서는 AHM과 같이 Michael 부가반응성이 있는 acrylate기와 Michael 부가반응성이 없는 methacrylate기를 각각 1개씩 가지는 AHM을 사용하는 것이 필요함을 확인하였다.

Keywords: michael addition reaction; silica; silane coupling agent; FTIR; CP/MAS NMR.

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  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
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This Article

  • 2012; 36(5): 668-676

    Published online Sep 25, 2012

  • Received on May 3, 2012
  • Accepted on May 29, 2012