芴衍生物的合成及研究进展

讨论了芴的衍生物在精细化学、高分子合成及生物化工等领域的应用及其现有的合成方法 ,简要介绍了芴酮、碱金属芴的衍生物、芴甲醇、9,9-双 (甲氧基甲基 )芴等芴的衍生物的应用的进展情况。     

有机电致发光材料芴衍生物的合成

芴衍生物被认为是很有开发前景和实用价值的一类发光材料,它具有较为优异的综合性能,如良好的发光效率,较好的热稳定性等。本研究工作采用条件温和、产率较高的合成路线,对芴为单体进行官能团修饰,制备了9,9-二甲基芴、9,9-二甲基-2-硝基芴、9,9-二甲基-2-氨基芴、N-（4-联苯基）-9,9-二甲基-2-氨基芴。并对影响反应的重要因素进行了考察和讨论。     

三芴胺化合物、三芴胺聚合物发光材料及制备方法和应用

本发明公开了一种三芴胺化合物、三芴胺聚合物发光材料及制备方法和应用,该材料以三芴胺为骨架,通过改变含三芴胺聚合物发光材料侧链的化学结构可以调控发光材料的双极性和发光颜色;化学结构如右所示,制备方法是以芴作为最初的反应原料,通过一系列的简单反应,     

二苯基-2-(9,9'-螺二芴基)膦的合成与表征

以溴苯为起始原料,经过格氏反应,偶联反应,加成反应,酸催化闭环合成了2-溴-9,9'-螺二芴,最后与二苯基膦锂锂化反应合成目标化合物二苯基-2-(9,9'-螺二芴基)膦,总收率为60.6%。通过1H NMR确证了目标化合物的结构。     

一例基于芴的肟化合物的合成及离子选择性研究

利用2,7-二(4-苯甲醛)-9,9-二(乙基)芴、盐酸羟胺和三乙胺为原料,合成了一例基于芴的肟化合物,并对该化合物的结构进行了红外、核磁表征;通过紫外-可见光谱研究了该肟化合物对不同离子的选择性识别,并探索了其它离子对ClO-的干扰情况。     

Cadogan反应还原2-硝基苯基芴得咔唑

由Cadogan反应,2-硝基联苯在有机磷试剂存在下,硝基被还原成环得到咔唑类化合物得到启发,设计两步反应,第-步邻溴硝基苯与9,9-二甲基2-芴硼酸为原料经Suzuki偶联反应,甲苯中回流,得到芴与2-硝基苯的C—C偶联化合物;第二步Cadogan环化反应,三苯基膦还原2-（2-硝基苯）-9,9-二甲基芴得咔唑。这-设计重点在于合成咔唑的同时成功地引入了芴核,新合成的化合物通过共用苯环而包含了咔唑和芴。尽管用Cadogan反应还原2-（2-硝基苯）-9,9-二甲基芴时有两种关环可能,但该方法仍然简单有效,易于控制。副产品包括三苯基氧化膦和咔唑异构体12,12-二甲基-11,12-二氢茚[2,1-al咔唑非常容易通过柱层析除去。     

N~3,N~6-二(9,9-二甲基芴-2-基)-N~3,N~6-二(9-苯基咔唑-3-基)-9-苯基咔唑-3,6-二胺的合成

以3,6-二溴-9-苯基咔唑和N-(9,9-二甲基芴-2-基)-9-苯基咔唑-3-胺为原料,经Buchwald-Hartwig偶联反应,合成了一种含芴咔唑类空穴传输材料N~3,N~6-二(9,9-二甲基芴-2-基)-N~3,N~6-二(9-苯基咔唑-3-基)-9-苯基咔唑-3,6-二胺。利用~1H NMR、~(13)C NMR和IR等分析方法对产物结构进行了表征,并通过DSC-TG、UV-Vis和荧光光谱研究了物质的热稳定性和光学性能。     

油墨用酚醛树脂的化学改性研究

对油墨用(烷基)酚醛树脂的化学改性研究进行了综述.分别讨论了(烷基)酚醛树脂的环氧化改性、松香改性、石油树脂改性及其他含不饱和键的化合物或聚合物改性,主要包括改性原理、改性方法及其应用情况.     

油墨用酚醛树脂的化学改性研究

对油墨用(烷基)酚醛树脂的化学改性研究进行了综述。分别讨论了(烷基)酚醛树脂的环氧化改性、松香改性、石油树脂改性及其他含不饱和键的化合物或聚合物改性,主要包括改性原理、改性方法及其应用情况。     

油墨用酚醛树脂的化学改性研究

对油墨用(烷基)酚醛树脂的化学改性研究进行了综述.分别讨论了(烷基)酚醛树脂的环氧化改性、松香改性、石油树脂改性及其他含不饱和键的化合物或聚合物改性,主要包括改性原理、改性方法及其应用情况.     

Curing kinetics and properties of epoxy resin-fluorenyl diamine systems

Diglycidyl ether of bisphenol fluorene (DGEBF), 9,9-bis-(4-aminophenyl)-fluorene (BPF) and 9,9-bis-(3-methyl-4-aminophenyl)-fluorene (BMAPF) were synthesized to introduce more aromatic structures into the epoxy systems, and their chemical structures were characterized with FTIR, NMR and MS analyses. The curing kinetics of fluorenyl diamines with different epoxy resins including DGEBF, cycloaliphatic epoxy resin (TDE-85) and diglycidyl ether of bisphenol A (DGEBA) was investigated using non-isothermal differential scanning calorimetry (DSC), and determined by Kissinger, Ozawa and Crane methods. The thermal properties of obtained polymers were evaluated with dynamic mechanical thermal analysis (DMTA) and thermogravimetric analysis (TGA). The results show that the values of activation energy (E_a) are strongly dependent on the structures of epoxy resin and curing agent. The curing reactivity of epoxy system is restrained by the introduction of rigid fluorene into chain backbone and flexible methyl into side groups. The cured DGEBF/fluorenyl diamine systems exhibit remarkably higher glass transition temperature, better thermal stability and lower moisture absorption compared to those of DGEBA/fluorenyl diamine systems, and display approximate heat resistance and much better moisture resistance relative to those of TDE-85/fluorenyl diamine systems.     

含芳醚芴二胺/环氧树脂固化反应动力学及性能研究

以9,9-双[4-4-氨基苯氧基苯基]芴(BAOFL)作为固化剂,采用非等温DSC技术,研究了BAOFL/环氧树脂(E-51、TDE-85和芴基环氧树脂)体系的固化反应动力学,利用动态热机械分析仪(DMA)和热重分析仪(TGA)测试了固化树脂的力学性能和热稳定性。结果表明,固化反应活化能与环氧树脂和固化剂的结构密切相关,芳醚的引入提高了氨基与环氧基的反应性,固化树脂呈现出优良的热性能和力学性能,其玻璃化转变温度(T)达到206~248℃,贮能模量为2.54~2.94 GPa,初始热分解温度312~375℃,700℃g时的残炭率达到15.2%~31.7%。()     

Preparation and properties of one epoxy system bearing fluorene moieties

Diglycidyl ether of bisphenol fluorene (DGEBF) and 9,9‐bis(4‐aminophenyl) fluorene (BPF) were synthesized to introduce more aromatic structures into an epoxy system, and their chemical structures were characterized with Fourier transform infrared spectroscopy, NMR, and mass spectrometric analysis. The dynamic curing behavior of the DGEBF/BPF system was investigated with differential scanning calorimetry. DGEBF was cured with BPF, diaminodiphenylsulfone (DDS), and diaminodiphenylmethane (DDM), and E‐44 (bisphenol A epoxide) was also cured with BPF for comparison. The thermal properties of the obtained polymers were evaluated with dynamic mechanical thermal analysis and thermogravimetric analysis. The cured DGEBF/BPF system showed a remarkably higher glass‐transition temperature, better thermal stability and lower moisture absorption in comparison with the general bisphenol A epoxy resin/BPF system but approximated the heat resistance of the DGEBF/DDS and DGEBF/DDM systems. Such properties make this epoxy system very promising for heat‐resistant applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New fluorene‐based thermally stable five‐ and six‐membered rings polyimides with enhanced solubility

A novel ester diamine, 9‐(3,5‐diaminobenzoyloxy) fluorene, as a new monomer for preparation of polyimides was synthesized via two successive reactions. In the first step, reaction of 3,5‐dinitrobenzoylchloride with 9‐hydroxy fluorene in the presence of sodium hydroxide led to preparation of 9‐(3,5‐dinitrobenzoyloxy) fluorene. Second reaction was reduction of the nitro groups by tin (II) chloride and fuming hydrochloric acid to produce 9‐(3,5‐diaminobenzoyloxy) fluorene. The new diamine containing bulky fluorene group was characterized and polycondensed with different dianhydrides via two methods to produce polyimides. The new five‐membered and six‐membered ring polyimides were characterized and their properties including solubility behavior, inherent viscosity, thermal behavior and stability, and crystallinity were studied. They exhibited favorable balance of physical and thermal properties and their solubility were improved without sacrificing their thermal stability. Six‐membered rings polyimides showed higher thermal stability and lower solubility in comparison to related five‐membered ring polyimides. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

5-溴-7,7-二甲基-7H-苯并[C]芴的合成

以1-溴萘为原料,合成了5-溴-7,7-二甲基-7H-苯并[C]芴,总产率为63.1%。其中,对中间体2-(1-萘基)苯甲醛、7-甲基-7H-苯并[C]芴和7,7-二甲基-7H-苯并[C]芴的合成工艺进行了优化。优化反应条件为:2-(1-萘基)苯甲醛合成中,催化剂Pd(dppf)Cl2质量分数3.0%,反应温度40℃,反应时间2 h,产率96.8%;7-甲基-7H-苯并[C]芴合成中,催化剂Amberlyst 15型离子交换树脂的质量分数0.6%,反应温度110℃,反应时间4 h,产率95.4%;7,7-二甲基-7H-苯并[C]芴合成中,n(对甲苯磺酸甲酯)∶n(7-甲基-7H-苯并[C]芴)=2.5∶1,反应温度40℃,产率91.0%。产品结构通过1HNMR和ESI-MS进行了表征。     

固载杂多酸催化合成双酚芴

以固载磷钨酸为催化剂,芴酮和苯酚为原料催化合成了双酚芴,考察了影响反应的因素,采用FTIR、NMR和MS对产品结构进行了表征,并对自制双酚芴环氧树脂的湿热性能进行了评价。实验结果表明,活性炭固载磷钨酸用于催化合成双酚芴,催化活性高,催化剂易于回收。当固载磷钨酸用量为反应物总质量的15%,n(苯酚)∶n(芴酮)=10∶1,助催化剂β-巯基丙酸用量为0.2mL,反应温度95℃,反应时间12h时,经甲苯重结晶,双酚芴产品的质量分数及收率分别可达99.1%、81.5%。当共混树脂中芴基环氧树脂的质量分数为50%时,二氨基二苯砜(DDS)固化E-44、AG-80和F-44共混树脂的吸水率分别比纯树脂下降了15%、25%、28%,其中F-44共混树脂的玻璃化转变温度提高了近50℃,表明双酚芴作为环氧树脂单体可明显改善树脂的湿热性能。     

Fine dispersion of carbon black in fluorene‐based resin

The dispersion ability of fluorene‐based epoxy resin (FBE), bisphenol A based epoxy resin (PBE), fluorene‐based polyester (FBP), and polycarbonate (PC) in carbon black (CB) was evaluated. CB/FBE composite had a lower L value (reflectance, blackness) than that of CB/PBE composite, for the same CB content. Aggregations of CB in CB/FBE composites were much smaller than those in CB/PBE composites. The strong interaction between fluorene with cardo structure and CB resulted in a fine dispersion of CB in FBE. FBP had much higher dispersion ability of CB than PC. CB (50 wt%) was dispersed into FBP compared with the 10 wt% of CB dispersed in PC by melt blending. The effect of CB on the mechanical properties of FBP was much higher than that on PC due to fine dispersion of CB in FBP. The effect of CB addition on the T_g of FBP was also higher than that of CB on the T_g of PC. Computational simulation indicates that most stable energy between fluorene with a cardo structure and graphite structure was smaller than the energy between bisphenol A and graphite. It was also shown that the minimum energy appeared when the fluorene structure was almost parallel to the graphite plane. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and properties of fluorene‐based polyimide adhesives

Five kinds of fluorene‐based polyimides (PIs) based on 4,4′‐oxydiphthalicanhydride (ODPA), 9,9′‐bis(4‐aminophenyl)fluorene (BAFL), and 3,4′‐diaminodiphenyl ether (3,4′‐ODA) were synthesized through two‐step method. The partially or fully imidized PI films were cast from poly(amic acid) (PAA) solution and were imidized by far‐infrared radiation at various temperatures. The degree of imidization was characterized by FT‐IR and TGA. The fully imidized PI films were characterized by DMTA, TGA, and tensile tests. The partially imidized PI films were adhered to stainless steel plates for preparing the single lap joints. Lap shear strength (LSS) at room temperature was measured to compare the adhesive strength of single lap joint. Fractured surfaces were analyzed using scanning electron microscopy (SEM). The effects of fluorene content on thermal, tensile, and adhesion properties of PIs were elaborately studied. The results showed that PI films exhibited high glass transition temperature (T_g), good thermalplasticity, and thermal stability. The LSS of PIs increased abruptly with the incorporation of fluorene groups. The LSS of PI‐50/50 was the highest, which was 22.3 MPa. The LSS of PI‐50/50 was also measured at high temperature to investigate the thermal resistance of fluorene‐based PI adhesive. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

一种新型高吸水性树脂的制备

以高锰酸钾为引发剂制备了玉米淀粉和丙烯酰胺的接枝共聚物，并将共聚物水解制得一种新型高吸水性树脂，考察了聚合条件和水解条件对树脂性能的影响，并对该树脂的吸水率，保水率，热稳定性进行了测定，结果表明，该树脂最高吸水率可达1100倍以上。     

Carbazole/fluorene copolymers with dimesitylboron pendants for blue light-emitting diodes

A series of random and alternating carbazole/fluorene copolymers with various dimesitylboron-containing carbazole derivative contents were synthesized by Suzuki polymerization for use as a light-emitting layer in blue light-emitting diodes. Two carbazole derivatives, CzPhB and CzPhThB consisted of a carbazoyl group as the donor and a dimesitylboron group as the acceptor group, separated by phenyl and phenyl-thiophene groups π-conjugated systems, respectively. The copolymers exhibited good thermal stability and blue emission in both solution and the solid state. Moreover, the CzPhB/fluorene and CzPhThB/fluorene copolymers exhibited a higher PL quantum efficiency than the fluorene-based homopolymer (POF). Higher brightness and larger current efficiency were observed for the CzPhB/fluorene and CzPhThB/fluorene copolymer-based devices compared to the POF-based device. Additionally, the CzPhThB/fluorene copolymer-based devices had better EL performances than the CzPhB/fluorene copolymer-based devices. The turn-on voltage, maximal brightness, and highest luminescence efficiency of the carbazole/fluorene copolymer-based devices were found to be 4.5-8.5 V, 436 cd/m², and 0.51 cd/A, respectively.