高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (6): 1431.

• 研究论文 • 上一篇    下一篇

乙酸乙酯在D3F阴离子开环聚合中的促进作用

杨鹏, 高亚娟, 管涌, 郑安呐   

  1. 华东理工大学材料科学与工程学院, 上海先进聚合物材料重点实验室, 超细材料制备与应用教育部重点实验室, 上海 200237
  • 收稿日期:2010-06-17 修回日期:2010-08-16 出版日期:2011-06-10 发布日期:2011-05-10
  • 通讯作者: 郑安呐 E-mail:zan@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 5093302)和上海市重点学科建设项目(批准号: B502)资助.

Promoting Effect of Ethyl Acetate on Anionic Ring-opening Polymerization of l,3,5-Trimethyl-l,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane(D3F)

YANG Peng, GAO Ya-Juan, GUAN Yong, ZHENG An-Na*   

  1. Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2010-06-17 Revised:2010-08-16 Online:2011-06-10 Published:2011-05-10
  • Contact: ZHENG An-Na E-mail:zan@ecust.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 5093302)和上海市重点学科建设项目(批准号: B502)资助.

摘要: 采用硅醇钠为引发剂,乙酸乙酯(EA)为极性调节剂,在HAKKE转矩流变仪中聚合为聚三氟丙基甲基硅氧烷(PMTFPS),并探讨了三氟丙基甲基环三硅氧烷(D3F)聚合过程中EA的促进作用。结果表明:在120℃下,EA极性调节剂浓度为0.30mol/ L,反应4 min时,PMTFPS的数均分子量( )达到最大,为2.45×105,产率为89.2 wt%。通过激光飞行质谱(MALDI-TOF-MS)分析可知此反应条件下环状硅氧烷副产物含量较低,仅为0.75 wt%,说明此条件下链反咬等副反应得到很好地抑制。差示扫描量热法(DSC)和热失重分析(TGA)表明PMTFPS可以在较宽的温度范围内使用。

关键词: 氟硅聚合物, 乙酸乙酯;阴离子开环聚合;转矩流变仪

Abstract: Poly[methyl(trifluoropropyl)siloxane](PMTFPS) was prepared in the mixing chamber of a HAAKE torque rheometer using sodium silanolate as the initiator, and ethyl acetate(EA) as the promoter. The promoting effect of EA in the anionic bulk polymerization of D3F was investigated. The results show that the maximum of number average molecular weight(Mn=2.45×105) of PMTFPS was obtained with high yield(89.2%) when the polymerization was carried out in the presence of 2.74%initiator and 0.30 mol/L EA at 120 ℃ for 4.0 min. The backbiting reactions were almost suppressed and 0.74% cyclic by-products were obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry(MALDI-TOF-MS) for EA promoter system. Investigations of differential scanning calorimetry(DSC) and thermogravimetic analysis(TGA) show that PMTFPS can be used in a wide range of operational temperatures.

Key words: Poly[methyl(trifluoropropyl)siloxane], Ethyl acetate, Anionic ring-opening polymerization, Torque rheometer

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