9,9-二(丙酸六氟丁酯)芴共聚物的合成及荧光性能

采用迈克尔加成反应合成了含氟芴单体2,7-二溴-9,9-二(丙酸六氟丁酯)芴(FHFBP),进一步采用铃木反应制备了不同FHFBP结构单元含量的9,9-二(丙酸六氟丁酯)芴-9,9-二辛基芴共聚物(PF8FHFBP)。通过红外光谱、核磁氢谱、紫外光谱和荧光光谱等方法对其结构和性能进行了表征。结果表明,成功合成了相对分子质量较高的含氟聚芴PF8FHFBP,并且在甲苯、四氢呋喃(THF)和氯仿等常用的有机溶剂中具有良好的溶解性。含氟侧链的引入有效地提高了聚合物的疏水性,但使得波长440 nm处聚芴的荧光峰渐渐消失,在530 nm附近出现了1个新的峰。可能是含氟侧链的引入使聚合物侧链产生结晶现象,主链之间更加致密的堆砌产生出激基缔合物,通过不同浓度共聚物溶液的荧光光谱与共聚物的差示扫描量热测试作了进一步分析讨论。     

蓝光材料双亲共聚芴的合成、表征与性能

通过Suzuki缩聚方法,将单体2,7-二溴-9,9'-二-(3,6-二氧烷基)芴和9,9'-二辛基芴-2,7-二-(三亚甲基硼酸酯)合成了一种新型的蓝光材料-双亲芴基共聚物.采用1H NMR、13C NMR和元素分析对共聚芴结构进行了表征;通过GPC、DSC和TGA测试,共聚芴有较高的分子量和较窄的分子量分布,同时还有很好的热稳定性.对共聚芴的紫外吸收光谱分析表明,在甲苯溶液和薄膜中的波长分别为389nm和393nm;对共聚芴的荧光发射光谱分析表明,在甲苯溶液和薄膜中的波长分别为415nm和437nm.     

羟乙基聚芴材料合成与表征

以2,7-二溴-9,9-二(2-羟乙基)-芴和2,7-双硼酸酯-(9,9-二辛基芴)为单体,通过Suzuki聚合反应合成一种蓝光聚(9,9-二羟乙基-2,7-芴)-2,7-(9,9-二辛基芴)(PFOH),采用1HNMR和热重分析对其进行表征,PFOH聚合物具有良好的热稳定性,通过紫外-可见吸收光谱(UV-vis)、光致发光光谱(PL)表征了聚合物的光物理性能,采用循环伏安法通过计算得知聚合物PFOH光学带隙Eg为2.90eV,EHOMO=-5.46eV,ELOMO=-2.56eV。     

聚芴/无机粒子纳米复合材料的制备及其光致发光研究

从2,7-二溴芴出发合成9,9-二辛基聚芴(POF),在球状SiO2、多孔SiO2、TiO2、未改性Al2O3和改性Al2O3纳米粒子中筛选出有良好溶解性的改性Al2O3纳米微粒制备POF/Al2O3纳米复合材料.研究表明POF/Al2O3纳米复合膜的成膜性好,荧光发射光谱相对于POF膜有明显的蓝移,发光峰波长不随激发波长移动,有很好的荧光特性.     

基于圈形二胺的六元环聚酰亚胺共聚物膜的制备与气体分离性能研究

以2,7-二硝基-9-芴酮和苯酚作为原料，通过两步反应合成了一种含羟基的圈形二胺单体2,7-二氨基-9,9-双(4-羟苯基)芴(BHPDAF)。将其与9,9-双(4-氨基苯基)芴(BAPF)和1,4,5,8-萘四甲酸二酐(NTDA)在间甲酚中进行无规共聚，通过控制两种二胺单体之间的摩尔比(BHPDAF/BAPF=1/2,1/1,2/1)合成了三种具有不同羟基含量的新型六元环聚酰亚胺共聚物[NTDA-BHPDAF/BAPF(1/2,1/1,2/1)]。这些聚酰亚胺共聚物在间甲酚、1-甲基吡咯烷酮(NMP)、N,N-二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)和γ-丁内酯(GBL)等有机溶剂中具有良好的溶解性。用溶液浇铸法制得了具有良好力学性能的薄膜，其拉伸强度为59.6M～70.2MPa,断裂伸长率为16.8%～26.6%。热重分析结果表明，这些聚酰亚胺共聚物膜的5%热失重温度(T_d5)均超过480℃。气体分离性能测试结果表明，共聚物膜均具有良好的气体分离性能。例如：NTDA-BHPDAF/BAPF(2/1)薄膜在35℃和202kPa(膜两侧压差)条件下的CO     

通过格氏反应制备羧酸烷基芴的方法研究

以9,9-二己基-2,7-二溴代芴和干冰为原料,无水四氢呋喃为溶剂,在一定条件下通过格氏反应制备了2,7-二羧酸-9,9-二己基芴,收率58%.探讨了反应原料、引发剂、溶剂等方面因素对反应的影响.     

一种基于D-π-A型芴衍生物的合成、核磁共振谱及光谱性能研究

合成了一种具有D-π-A结构特征的新型芴衍生物:2-(2,4-二氟苯基)-7-(4-甲氧基苯基)-9,9-二辛基芴(1)。通过元素分析、红外光谱(IR)以及全面的一维核磁共振氢谱(1 H NMR)、碳谱(13 C{1 H}NMR)、氟谱(19F{1 H}NMR)对其结构进行了全面表征。通过优化反应物的投料顺序,得到较为合理的合成方法。详细分析了核磁共振谱谱线特征。利用紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明,在CH2Cl2溶液中,化合物1在300~330nm波段有吸收峰,归属于π-π*跃迁;其光学带隙Eg为3.39eV,发射峰值位于383nm,并且具有强烈的深蓝色荧光发射(激发波长为310nm),在CH2Cl2溶液中量子效率达到0.70。此外,化合物1的吸收和发射光谱具有溶剂极性依耐性。     

具有深蓝色荧光的分子内电荷转移型三聚体的合成

高效稳有机蓝色荧光材料可以应用于白色光源和全色显示器件。设计合成了具有深蓝色荧光的三聚体3,7-双(9,9-二己基芴基)-2,8-二环己甲氧基-S,S-二氧化二苯并噻吩(FSOCyF)。首先在S,S-二氧化二苯并噻吩(SO)的2,8-位引入官能团环己甲氧基,以增加二苯并氧化噻吩的溶解性,将可溶性的二苯并氧化噻吩溴化后,与9,9-二己基芴-2-硼酸在钯催化下进行Suzuki-coupling反应,合成了分子内电荷转移型三聚体FSOCyF,并运用核磁共振氢谱/碳谱、元素分析、基质辅助激光解吸电离飞行时间质谱,X射线衍射以及荧光光谱对其结构和发光性能进行表征。     

磺酸型聚芴的合成及性能

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)芴单体,并通过Suzuki偶合反应制备了含不同磺酸比例的磺酸型聚芴(PF6SO3H)。通过核磁共振氢谱、凝胶渗透色谱、溶解性试验、紫外吸收光谱、荧光发射光谱、循环伏安曲线及热重分析法对聚合物结构和性能进行了表征分析。结果表明,成功合成了相对分子质量在3万~5万之间的磺酸型聚芴。发现随着磺酸型聚芴中磺酸基团含量的不同,聚合物在甲醇溶液中的溶解度不同,含有50%磺酸基团的PF6SO3H在甲醇中的溶解度达到了18mg/mL。磺酸侧链的引入使聚芴在薄膜状态和溶液状态下的紫外吸收最大吸收峰和最大荧光发射峰较聚(9,9-二己基)芴(PF6)发生了9nm~40nm红移,且能带隙逐渐变窄,同时磺酸型聚芴的HOMO较PF6增大。热失重分析发现磺酸侧链的引入,使得磺酸型聚芴的热稳定性较PF6有一定的下降。     

新型POSS基有机/无机杂化分子发光材料的制备及聚集效应研究

有机发光材料在电致发光与显示器件领域有着非常广泛的应用。以具有高荧光量子产率的长共轭芴类衍生物2-乙炔基-7-(4-(4-甲氧基苯乙烯基)苯乙烯基)-9,9-二辛基芴(EMOF)和POSS(T8H8)为原料,通过硅氢化反应制备了POSS基有机/无机杂化分子发光材料(EMOF-POSS),并用FT-IR、1H-NMR和13C-NMR对其结构进行了表征。通过紫外-可见和荧光光谱研究了EMOF和EMOF-POSS在不同比例的THF/H2O混合溶剂中的聚集效应,并对两者的热性能进行了测试。结果表明,EMOF-POSS不仅具有较好的热稳定性,而且有效地降低了荧光生色团的聚集,从而提高了材料的荧光量子产率(ΦFL)和发光性能。     

Synthesis and electrochemical polymerization of 9,9-bis(carbazolylalkyl)fluorene and characterization of its conducting polymer film with high tensile strength

Free-standing poly(9,9-bis(carbazolylalkyl)fluorene) (P2Cz-A-F, alkyl = hexyl or dodecyl) films with high tensile strength (185–200 kg cm⁻²) were electrochemically synthesized by direct anodic oxidation of the monomer 9,9-bis(carbazolylalkyl)fluorene (2Cz-A-F) in a mixed electrolyte of boron trifluoride diethyl etherate containing 30% CH₂Cl₂ (by volume). The electrochemical and physical properties show that the quality of P2Cz-A-F films are much better than that of polycarbazole (PCz) and polyfluorene (PF) films due to the specially designed structure consisting of stiff bicarbazyl chromophores linked by a flexible long alkyl spacer at the fluorene unit. The structure of free-standing P2Cz-A-F films was investigated by UV–visible and infrared spectroscopy. Thermal analysis shows that the polymer films have good thermal stability. Fluorescent spectral studies indicate that polymer films in the solid state are blue-light emitters, which may meet potential applications in polymer light-emitting diodes.     

具有光学性能的含芴聚亚胺酮的合成与表征

以含芴芳香二胺和2,7-二溴-9-芴酮为单体,通过Buchwald-Hartwig交叉偶联反应缩聚合成了含芴聚亚胺酮(PIKF)。聚合物结构经核磁共振(1H-NMR)、红外光谱(FT-IR)及元素分析得以确认。通过凝胶渗透色谱(GPC)、差示扫描量热分析(DSC)、热重分析(TG)和X射线衍射(XRD)等对其性能进行测试,结果表明该类聚合物具有较高的分子量(-Mw>3.0×104)以及良好的热稳定性(T5%>310℃),在40℃～350℃的范围内没有观测到玻璃化转变;XRD显示PIKF为无定型结构,因而具有良好的溶解性能。另外,利用紫外、荧光等对其光学性能进行了测试,在四氢呋喃(THF)中的UV-vis的最大吸收波长为271 nm和369 nm左右,最大荧光发射波长分别在445 nm和455 nm。     

Synthesis and light-emitting properties of poly[9-(4′-tert-butyl-phenylenemethene)-fluoroene-co-9,9-dioctylfluorene]

A novel copolymer, poly[9-(4′-tert-butyl-phenylenemethene)-fluoroene-co-9,9-dioctylfluorene], has been synthesized through the Yamamoto coupling method. The copolymer has good solubility and thermal stability with a glass transition temperature at 85 °C. The PL spectrum of the copolymer shows a maximum emission peak at 530 nm. A polymer light-emitting diode (PLED) with the configuration ITO/PEDOT/copolymer/Ca/Al has been fabricated. The device emits green light with an emission peak at 540 nm. A maximum brightness of 603 cd/m² was achieved at a drive voltage of 24.3 V.     

Excited-state absorption and anisotropy properties of two-photon absorbing fluorene derivatives

The electronic structure of fluorene derivatives N-(7-benzothiazol-2-yl-9,9-bis-decyl-9H-fluoren-2-yl)-acetamide (1); 9,9-didecyl-2,7-bis-(N,N-benzothiazoyl)fluorene (2); 4,4'-{[9,9-bis(ethyl)-9H-fluorene-2,7-diyl]di-2,1-ethenediyl}bis(N,N-diphenyl)benzeneamine (3); and 4,4',4"{[9,9-bis(ethyl)-9H-fluorene-2,4,7-triyl]tri-2,1-ethenediyl}tris(N,N-diphenyl)benzeneamine (4) were investigated by a steady-state spectral technique, quantum-chemical calculations, and a picosecond pump-probe method. These derivatives are of interest for their relatively high two-photon absorption. The steady-state excitation anisotropy spectra reveal the nature of the ground-state absorption bands. Semiempirical quantum-chemical calculations of the fluorene derivatives (AM1, ZINDO/S) show good agreement with experimental data. The spectral positions and alignment of various electronic transitions of derivatives 1-4 were estimated from their excited-state absorption and anisotropy spectra.     

Optical and electronic properties of fluorene/thiophene/benzothiadiazole pseudorandom copolymers for photovoltaic applications

A new family of 9,9-bisalkylfluorene (F)/thiophene (T)/benzothiadiazole (B) π-conjugated copolymers for organic solar cells is reported. The structure of the reported copolymers is pseudorandom: in turn each F, T, B monomer unit is alternated to the other randomly distributed two units. Voltammetric, UV–visible, and photoluminescence measurements have been carried out to assess the optical and electronic properties of the synthesized materials. The occurring of photoinduced charge transfer towards a fullerene electron acceptor was investigated by photoluminescence quenching and light-induced electron spin resonance experiments. The copolymer having alternating thiophene monomer units and randomly distributed fluorene and benzothiadiazole units exhibits the most promising characteristics; the photophysic study shows that such polymer/fullerene blend could represent a novel and cheaper material to be used as convenient donor–acceptor system for polymer solar cells.     

White polymer light-emitting diodes based on poly(2-(4′-(diphenylamino)phenylenevinyl)-1,4-phenylene-alt-9,9-n-dihexylfluorene-2,7-diyl) doped with a poly(p-phenylene vinylene) derivative

Efficient white polymer light-emitting diodes based on the polymer blend of poly(2-(4′-(diphenylamino)phenylenevinyl)-1,4-phenylene-alt-9,9-n-dihexylfluorene-2,7-diyl) doped with poly{2-[3′,5′-bis(2?-ethylhexyloxy) benzyloxy]-1,4-phenylenevinylene}-co-poly(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene) were fabricated. The electroluminescence (EL) spectrum is easily controlled by changing the dopant concentration. A white light emission was realized on the device with the dopant concentration of 0.194‰ and the emission light is less sensitive to the applied voltage in a wide voltage range. The maximum luminance and the maximum EL efficiency of the single-layer device were 2330 cd/m² and 0.29 cd/A, respectively. By introducing an Alq₃ layer as an electron transporting and hole blocking layer, the overall performance of the double layer device was dramatically improved, the maximum luminance and the maximum EL efficiency reached 3300 cd/m² and 2.37 cd/A, respectively.     

N-异丙基丙烯酰胺共聚物的温敏性

采用自由基水溶液聚合方法制备出了N-异丙基丙烯酰胺(N IPA)温敏共聚物P(AM-N IPA);首次在P(AM-N IPA)结构中引入丙烯酸钠(N aAA)单体结构单元,合成了离子型共聚物P(AM-N IPA-N aAA);考察了共聚物P(AM-N IPA)和P(AM-N IPA-N aAA)溶液温敏性的影响因素;分别采用荧光光谱分析法以及乌氏黏度计稀释法对共聚物溶液温敏机理进行了研究。结果表明,不同共聚单体的配比以及单体含量对共聚物溶液低临界溶解温度(LCST)均有显著影响;当温度高于共聚物低临界溶解温度时,共聚物分子链上的疏水基团的缔合作用增强,导致疏水聚集结构的形成,聚合物分子链发生去溶剂化作用,在共聚物稀溶液中表现为线团收缩,在共聚物亚浓溶液中表现为共聚物分子间聚集发生相分离。     

含芴结构环氧树脂的合成与性能

合成了一种耐湿热性能优异的环氧树脂9,9-二 芴,通过对环氧化反应影响因素的讨论确定了最佳的环氧化反应条件,使产物环氧值达到了理论值的97 ％。确定了纯的9,9-二 芴环氧树脂的固化工艺,并对其树脂浇注料的力学性能进行了评测。为研究9,9-二 芴对其它环氧树脂体系湿热性能的影响,对9,9-二 芴/AG-80树脂体系的吸水率进行了测定,并比较了该体系吸水前后玻璃化转变温度和模量的变化,从而证明了9,9-二 芴对提高环氧树脂耐湿热性能的作用。     

含噁二唑类与咔唑类共聚物的合成与表征

由2-苯基-5-〔甲基丙烯酰胺基取代苯基〕-1,3,4-噁二唑(OXD)与甲基丙烯酸乙基咔唑酯(CzE-MA)两种单体合成了含噁二唑和咔唑基团的无规共聚物。通过红外、核磁、紫外、荧光、热重、差示扫描量热,凝胶渗透色谱对聚合物进行了表征。测试结果表明共聚物有很好的溶解性,均可溶于常用的有机溶剂,如THF,CHCl2,CHCl3等,其分子量在16950～22500之间。有良好的热稳定性和很高的玻璃化转变温度(Tg=190～222℃),最大吸收波长在220～340nm之间,具有良好的荧光性,其荧光发射波长均在372～451nm范围内,是一类蓝紫色荧光聚合物。共聚物随着CzEMA组分的减少和OXD组分的增加,发射波长蓝移,其中以P(OXD8-CzEMA2)的荧光性最好,荧光量子产率高达0.70。     

Blue organic light-emitting diodes based on solution-processed fluorene derivative

We report blue fluorescent organic light-emitting devices (OLED) by solution process utilizing a blue emitting small molecule, 2,7-bis[(9-ethyl-9H-carbazol-3-yl)ethenyl]-9,9-bis(4-n-octyloxyphenyl)-9H-fluorene (CB), which has good solubility in common organic solvent. The peak positions of absorption and emission spectra of a new fluorene-based molecule in tetrahydrofuran solution were observed at 399 and 439 nm, respectively. We achieved a maximum luminous efficiency of approximately 3 cd/A with CIE color coordinates of (0.15, 0.15) in our device.