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首页> 外文期刊>Polymer science, Series C >Synthesis and Gas-Separation Properties of New Silacyclopentane-Containing Polynorbornenes
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Synthesis and Gas-Separation Properties of New Silacyclopentane-Containing Polynorbornenes

机译：含含硅戊烷的多毒药植物的合成及气体分离性能

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摘要

Previously, it was shown that the presence of bulky silicon-containing substituents in the monomer unit of metathesis polynorbornenes hinders the postmodification and, in particular, exhaustive gem-difluorocyclopropanation of main-chain double bonds. In order to reduce the double bonds shielding by substituents, a new polynorbornene with a dimethylsilacyclopentane fragment in the monomer unit, poly(4,4-dimethyltricyclo[5.2.1.0(2,6)]-4-siladec-8-ene) (PNBCP), is synthesized, in which the silylmethyl group is moved further from the double bonds. In order to achieve this, the monomer 4,4-dimethyltricyclo[5.2.1.0(2,6)]-4-siladec-8-ene (NBCP) is first obtained via the diene condensation of 1,3-cyclopentadiene and 1,1-dichlorosilacyclopent-3-ene with following methylation of Si-Cl bonds. NBCP is polymerized by the ring-opening metathesis scheme in the presence of the first-generation Grubbs catalyst, Cl-2(PCy3)(2)Ru=CHPh. The new polymer PNBCP is obtained in a yield of 99-100% and characterized. The gem-difluorocyclopropanation of PNBCP with difluorocarbene, generated during the thermolysis of sodium chlorofluoroacetate, is studied; the conditions for exhaustive replacement of double bonds by gem-difluorocyclopropane are found. It is shown that PNBCP is more active in postmodification compared to poly(5-trimethylsilyl)norbornene but is less active than unsubstituted polynorbornene. It is demonstrated that the introduction of the silacyclopentane fragment into the monomer unit of the metathesis polynorbornene and its subsequent difluorocyclopropanation lead to increase in gas permeability and diffusion and cause a slight decrease in ideal separation selectivities. It is found that gem-difluorocyclopropanation increases the glass transition temperature of PNBCP by 60 degrees C and makes its films stable when stored in air.
机译：以前，结果表明，在复分解多冰片烯的单体单元中存在稀硅含硅的取代基阻碍了后修补，特别是具有主要链双键的详尽的Gem-Diflorcyclopanation。为了减少取代基屏蔽的双键，在单体单元中具有二甲基硅烷戊烷片段的新多冰片烯，聚（4,4-二甲基三酰基[5.2.1.0（2,6）] - 4-锡 - 8-eNE）（合成PNBCP），其中甲硅烷甲基进一步从双键移动。为了实现这一点，首先通过1,3-环戊二烯和1的二烯缩合获得单体4,4-二甲基三酰基[5.2.1.0（2,6）] - 4-硅烷烯-8-烯（NBCP）， 1-二氯硅酸盐-3-烯酮，其甲基化甲基键合。在第一代GRUBBS催化剂，CL-2（PCY3）（2）Ru = CHPH的存在下，通过开环复分解方案聚合NBCP聚合。新的聚合物PNBCP以99-100％的产率获得并表征。研究了在氯氟酯钠的热解期间产生的二氟乙烯PNBCP的宝石 - 二氟环丙烷;发现了GEM-二氟环丙烷彻底替代双键的条件。结果表明，与聚（5-三甲基甲硅烷基）降冰片烯相比，PNBCP在后修浆中更活跃，但比未取代的多冰冰硼烯较低。结果证明，将硅辛丁烷片段引入复分解多冰冰树脂的单体单元及其随后的二氟环丙烷导致液态渗透性和扩散的增加​​，并导致理想的分离选择性略微降低。发现宝石 - 二氟环丙烷将PNBCP的玻璃化转变温度提高了60℃，并使其薄膜储存在空气中时稳定。

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  • 来源
    《Polymer science, Series C》 |2019年第1期|共13页
  • 作者

    Zhigarev V. A.; Morontsev A. A.; Nikiforov R. Yu.; Gringolts M. L.; Belov N. A.; Komalenkova N. G.; Lakhtin V. G.; Finkelshtein E. Sh.;

  • 作者单位

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

    State Sci Res Inst Chem &

    Technol Organoelement C Moscow 105118 Russia;

    State Sci Res Inst Chem &

    Technol Organoelement C Moscow 105118 Russia;

    Russian Acad Sci Topchiev Inst Petrochem Synth Moscow 119991 Russia;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
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