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Hydrosilylation as an efficient tool for polymer synthesis and modification with methacrylates

机译：氢化硅烷化作为聚合物合成和用甲基丙烯酸酯改性的有效工具

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摘要

Hydrosilylation is a well-established reaction for the preparation of organo-silicon compounds, in which vinyl groups react with silanes (Si-H) usually catalysed by late transition metal complexes, most often Pt(II) complexes. Hydrosilylation of functional methacrylates provides access to functional poly(dimethylsiloxane)s (PDMS), from appropriate hydride terminated and functional PDMS, in very high yielding reactions without the formation of any side products, odour and without the need for labor-intensive purification. Herein, commercially available telechelic PDMS hydrides (h(2)PDMS) have been modified with a range of different methacrylates using very low catalytic amounts of commercial Pt(II) catalysts. The products have been characterized by H-1 and C-13 NMR, SEC, IR and MALDI-ToF MS demonstrating high selectivity and very high reaction yields. The versatility of hydrosilylation has been exploited for the preparation of ABA triblock copolymers using poly(ethylene glycol) methacrylate and more structurally demanding vinyl terminated methacrylic macromonomers as obtained by catalytic chain transfer polymerization (CCTP). H-1 NMR revealed the formation of solely anti-Markovnikov products and the high tolerance of the reaction towards other functionalities, such as epoxides present in glycidyl methacrylate. The specific Si-H signals in H-1 NMR (4.8 ppm) and IR (2126 cm(-1)) from the Si-H group allow for facile monitoring of the progress of the reaction. SEC and MALDI-ToF MS investigations further highlighted the formation of well-defined polymer systems with near perfectly matching molecular compositions.
机译：氢化硅烷化是制备有机硅化合物的良好反应，其中乙烯基与通常由晚期过渡金属配合物催化的硅烷（Si-H）反应，最常是Pt（II）配合物。功能性甲基丙烯酸酯的氢化硅烷化提供对功能性聚（二甲基硅氧烷）S（PDMS）的可接近的合适氢化物呈且功能PDMS，在非常高的氢化物中，在非常高的产生反应中，不形成任何侧面产品，气味，而无需劳动密集型纯化。在此，使用非常低催化量的商业Pt（II）催化剂，通过各种不同的甲基丙烯酸酯改性市售的Telechelic PDMS氢化物（H（2）PDMS）。该产品的特征在于H-1和C-13 NMR，SEC，IR和MALDI-TOF MS，展示了高选择性和非常高的反应产率。利用催化链转移聚合（CCTP）的甲基丙烯酸甲酯（乙二醇）甲基丙烯酸甲酯和更加结构要求乙烯基封端的甲基丙烯酸大分子单体制备氢化硅烷化的多功能性。 H-1 NMR揭示了仅抗马洛维肽产品的形成和对其他功能的反应的高耐受性，例如甲基丙烯酸缩水甘油酯中存在的环氧化物。 H-1 NMR（4.8ppm）和Ir（2126cm（-1）中的特异性Si-H信号来自Si-H组，允许容易地监测反应的进程。 SEC和MALDI-TOF MS调查进一步强调了近乎完全匹配的分子组合物的定义聚合物系统的形成。

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  • 来源
    《RSC Advances》 |2015年第8期|共7页
  • 作者

    Risangud Nuttapol; Li Zhijian; Anastasaki Athina; Wilson Paul; Kempe Kristian; Haddleton David M.;

  • 作者单位

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

    Univ Warwick Dept Chem Coventry CV4 7AL W Midlands England;

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