Photocontrolled Living Anionic Polymerization of Silicon-Bridged [1]Ferrocenophanes with Fluorinated Substituents: Synthesis and Characterization of Fluorinated Polyferrocenylsilane (PFS) Homopolymers and Block Copolymers
Photocontrolled Living Anionic Polymerization of Silicon-Bridged [1]Ferrocenophanes with Fluorinated Substituents: Synthesis and Characterization of Fluorinated Polyferrocenylsilane (PFS) Homopolymers and Block Copolymers
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DOI：
10.1002/macp.200900395
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发表时间：
2010-02
影响因子：
2.5
通讯作者：
Gregory S. Smith;S. Patra;Lawrence Vanderark;S. Saithong;J. Charmant;I. Manners
中科院分区：
文献类型：
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作者：
Gregory S. Smith;S. Patra;Lawrence Vanderark;S. Saithong;J. Charmant;I. Manners
Photocontrolled生活阴离子开环聚合(ROP)的紧张silicon-bridged [1] ferrocenophanes Fe(η- C 5 H 4) 2森那美(CH 2 CH 2 CF 3)(1)、铁(η- C 5 H 4) 2森那美(CH 2 CH 2 7 CF (CF 2) 3)(2)和铁(η- C 5 H 4) 2 Si-Me (CH 2 CH 2 CH 2 C 6 F(5)和3 (3),3,3-trifluoropropyl, heptadecafluoro-1, 1, 2, 2-tetrahydrodecyl,和pentafluorophenylpropyl其取代基,分别在硅、探索。因此，在5°C的THF中，由Na[c5h 5]引发的[1]二茂铁1-3的光控ROP合成了具有可控分子量和窄分子量分布（M w /Mn < 1.10）的明确的含氟均聚物[Fe(η- c5h 4) 2 Si(Me)R F] n (4-6) （R F =氢氟碳取代基）。顺序活性光解阴离子ROP允许合成定义明确的二嵌段共聚物，聚二茂铁基甲基苯基硅烷-嵌段聚二茂铁基甲基（3,3,3-三氟丙基）硅烷（PFMPS-b-PFS F） （7a-c），两嵌段的比例不同。DSC分析所得到的氟化二嵌段共聚物显示存在两个不同的玻璃化转变温度，表明两个嵌段的不混溶性。TEM分析显示，双嵌段共聚物7a-c在体中可预测自组装。通过测定氟化有机金属均聚物膜上的水接触角，研究了氟化有机金属均聚物疏水性的增强。
Photocontrolled living anionic ring-opening polymerization (ROP) of strained silicon-bridged [1]ferrocenophanes Fe(η-C 5 H 4 ) 2 SiMe(CH 2 CH 2 CF 3 ) (1), Fe(η-C 5 H 4 ) 2 SiMe(CH 2 CH 2 (CF 2 ) 7 CF 3 ) (2) and Fe(η-C 5 H 4 ) 2 Si-Me(CH 2 CH 2 CH 2 C 6 F 5 ) (3) with 3,3,3-trifluoropropyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, and pentafluorophenylpropyl hydrofluorocarbon substituents, respectively, on silicon, have been explored. Thus well-defined fluorine-containing homopolymers [Fe(η-C 5 H 4 ) 2 Si(Me)R F ] n (4-6) (R F =hydrofluoro-carbon substituents), with controlled molecular weights and narrow molecular weight distributions (M w /Mn < 1.10) were synthesized from the photocontrolled ROP of the respective [1]ferrocenophanes 1-3, initiated by Na[C 5 H 5 ] in THF at 5 °C. The sequential living photolytic anionic ROP allowed the synthesisof well-defined diblock copolymers, polyferrocenylmethylphenyl-silane-block-polyferrocenylmethyl(3,3,3-trifluoropropyl)silane (PFMPS-b-PFS F ) (7a―c), with different ratios of the two blocks. DSC analysis of the resulting fluorinated diblock copolymers showed the presence of two distinct glass transition temperatures suggesting the immiscibility of the two blocks. The diblock copolymers 7a―c undergo predictable self-assembly in the bulk as revealed by TEM analyses. The increased hydrophobicity of the fluorinated organometallic homopolymers was also studied by measuring the water contact angles on the homopolymer films.