CAJ | 학술논문

利用迈克尔加成反应合成了2,7-二溴-9,9-二-(3-丙基酰胺-2-甲基丙磺酸)芴(FSO3H),并通过Suzuki偶合反应制备了9,9-二-(3-丙基酰胺-2-甲基丙磺酸)芴-9,9-二己基芴共聚物(PF6SO3H)和9,9-二-(3-丙基酰胺-2-甲基丙磺酸)芴-4,4'-联苯共聚物(PFDBSO3H)。通过核磁共振氢谱(1H NMR)、凝胶渗透色谱(GPC)、紫外-可见吸收光谱对聚合物的结构进行了表征,利用荧光发射光谱对聚合物在各种条件下的荧光发光性能进行了研究。结果表明,上述两种磺酸型聚芴已被成功合成,这些聚合物具有较高的分子量并能够很好地溶于甲醇和水/醇混合溶剂中。荧光发光光谱研究表明：溶剂的极性、溶液的浓度和pH值、溶液中的金属离子都对磺酸型聚芴的发光性能有很大的影响。荧光发射光谱随着溶剂极性的增加逐渐红移。荧光强度随着溶液浓度的增加先增加后降低。当溶液pH从1增加到7.5时,荧光强度逐渐增加；当pH从7.5增加到12.5时,荧光强度降低直至猝灭。离子猝灭剂Mv+、Ag+、K+、Na+和Li+等对两种聚合物具有明显的猝灭效应,且对PF6SO3 H的猝灭效应比对PFDBSO3 H更强,这与磺酸型聚芴分子的刚性及离子的相互作用有关。
이용매극이가성반응합성료2,7-이추-9,9-이-(3-병기선알-2-갑기병광산)물(FSO3H),병통과Suzuki우합반응제비료9,9-이-(3-병기선알-2-갑기병광산)물-9,9-이기기물공취물(PF6SO3H)화9,9-이-(3-병기선알-2-갑기병광산)물-4,4'-련분공취물(PFDBSO3H)。통과핵자공진경보(1H NMR)、응효삼투색보(GPC)、자외-가견흡수광보대취합물적결구진행료표정,이용형광발사광보대취합물재각충조건하적형광발광성능진행료연구。결과표명,상술량충광산형취물이피성공합성,저사취합물구유교고적분자량병능구흔호지용우갑순화수/순혼합용제중。형광발광광보연구표명：용제적겁성、용액적농도화pH치、용액중적금속리자도대광산형취물적발광성능유흔대적영향。형광발사광보수착용제겁성적증가축점홍이。형광강도수착용액농도적증가선증가후강저。당용액pH종1증가도7.5시,형광강도축점증가；당pH종7.5증가도12.5시,형광강도강저직지졸멸。리자졸멸제Mv+、Ag+、K+、Na+화Li+등대량충취합물구유명현적졸멸효응,차대PF6SO3 H적졸멸효응비대PFDBSO3 H경강,저여광산형취물분자적강성급리자적상호작용유관。
2,7-dibromo-9,9-bis(3-propylamide-2-methylpropane sulfonic acid) fluorene ( FSO3 H) was synthesized by Michael addition reaction. Then, sulfonated polyfluorenes, poly[9,9-bis(3-pro-pylamide-2-methylpropane sulfonic acid) fluorene] -alt-poly(9,9-dihexyl-fluorene) (PF6SO3 H) and poly[9,9-bis(3-propylamide-2-methyl propane sulfonic acid) fluorene]-alt-poly(4,4’-diphen-yl) ( PFDBSO3 H) were synthesized by Suzuki Coupling. The structure and properties of sulfonated polyfluorenes were investigated by 1 H NMR, gel permeation chromatography ( GPC) and UV-visible absorption spectroscopy. Photoluminescence performances of polyfluorenes under various conditions were studied. The results show that these copolymers have high molecular weights and can dissolve in methanol and water/methanol mixture. The photoluminescent wavelengths of the sulfonated poly-fluorenes are red shifted with the increasing of polarity of the solvents. The fluorescence intensity of the polyfluorenes increases with the increasing of the polyfluorenes concentration under low concen-tration. Under high concentration, the quenching effect can be observed. A gradually increasing trend of fluorescence intensity is found when pH varied from 1 to 7 . 5 , and a reduction in fluores-cence intensity even completely quenching is observed when the pH changed from 7 . 5 to 12 . 5 . Ions, such as Mv+, Ag+, K+, Na+ and Li+ have quenching effects on the fluorescence of polyflu-orenes. The quenching effect of metal ions on PF6SO3 H shows much stronger than on PFDBSO3 H because of the more rigid backbone of PF6SO3 H and the interaction between the polymer and the ions.