新型含芴Schiff碱化合物的合成及其紫外-可见光谱性能研究

通过9-芴甲醛与相应的芳胺衍生物反应合成了两种新型含芴Schiff碱化合物:9-亚甲基19-亚(2-氨基芴)基芴和9-亚甲基-9-亚(2-甲基苯胺)基芴,其结构经核磁共振谱、红外光谱和质谱表征.吸收光谱法测定了两种含芴Schiff碱衍生物在乙醇、四氢呋喃、环己烷和氯仿中的最大吸收波长(λmax),并探讨了分子结构和溶剂...     

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。     

含芴功能材料的研究与应用

从芴的结构特点出发,讨论了芴的基本性质,包括化学结构特征、酸性与反应活性、热稳定性、光谱特征;综述了含芴结构的重要有机中间体,如芴酮、芴甲醇的化学特性与应用;综述了含芴结构的高分子材料改性单体,如双酚芴、9,9-双(3-氨基-4-羟苯基)芴等,以及它们在各种材料改性中的应用;介绍了含芴结构化合物在感光与光导材料领域的应用,如9,9-二烷基芴、芴-三苯胺结构化合物、芴-偶氮结构化合物;介绍了含芴结构的电致发光材料,如聚烷基芴、芴-噻吩共聚物、芴-噁二唑共聚物等;还介绍了含芴结构的医药与农药,如苯芴醇和含芴结构的植物生长激素;另外还介绍了用于催化剂领域的含芴功能化合物。     

2,7-二溴-9-亚(β-萘胺)基芴的合成

以芴为原料,通过空气氧化、水中溴代再与β-萘胺缩合,合成了2,7-二溴-9-亚(β-萘胺)基芴,较佳合成反应条件是:以四氢呋喃为溶剂,空气为氧化剂,n(芴):n(氢氧化钾)=1:2,室温反应6h,得芴酮,产率95.6%,再以芴酮为原料,水为溶剂,n(芴酮):n(溴)=1:2.5,回流反应10h,得2,7-二溴芴酮,然后以四氢呋喃为溶剂,冰乙酸为催化剂,n(2,7-二溴芴酮):n(β-萘胺)=1:1.3,回流反应12h,得2,7-二溴-9-亚(β-萘胺)基芴,产率为87.2%,所得产物的结构经IR、1HNMR、UV-Vis、MS和X射线单晶表征。     

3-溴螺环[芴-9,9'-氧杂蒽]的合成工艺研究

螺[芴-9,9'-氧杂蒽]衍生物作为蓝光材料或掺杂材料,被广泛应用于有机发光半导体(OLED)器件.本文以二苯醚为起始原料,经仲丁基锂锂化后,与3-溴-9H-芴酮反应得到中间体化合物,在二氯甲烷溶剂中,经对甲基苯磺酸催化闭环反应,合成了3-溴螺环[芴-9,9'-氧杂蒽].研究表明,当锂化反应温度为-45℃,原料n(二苯...     

具有芴酮结构聚芳亚胺的合成与性能研究

以含有芴结构的芳香二胺单体3,6二氨基-9-芴酮和不同结构的二溴化合物为底物,通过钯催化C-N交叉偶联缩聚反应合成了三种新型具有芴酮官能团的聚芳亚胺(PIKF)。其数均分子量(Mn)在3400~4300之间,重均分子量(Mw)在10200~13800之间,分散系数(Mw/Mn)为3.00~3.34。由TG和DSC测定了PIKF的耐热性能,该聚合物具有良好的耐热稳定性(Tg≥200℃,Td>500℃)。通过对PIKF的光学特性测定表明该聚合物具有良好光学性能,其UV-Vis最大吸收波长为455 nm和600 nm;最大荧光发射波长因PIKF结构的不同而不同,主要是由于不同聚合物主链结构π电子离域不同。     

2,7-二溴-9-二烷硫基亚叉芴的合成及表征

以芴为起始原料,合成了2,7-二溴-9-二甲硫基亚叉芴、2,7-二溴-9-二十二烷硫基亚叉芴、2,7-二溴-9-二苄硫基亚叉芴和2,7-二溴-9-二硫代乙烯撑亚叉芴4种新的芴衍生物.所得产物的结构经IR,NMR表征.     

双酚芴双醚酞酰亚胺的合成研究

就含有醚键的双酚芴型二酐单体的合成加以研究,本文利用芴酮和苯酚合成了双酚芴单体,在此基础上与50%的KOH溶液成盐,然后在相转移催化剂四丁基溴化胺的作用下与N-甲基-4-硝基酞酰亚胺发生亲核取代反应,生成比较重要的单体双酚芴型双醚酞酰亚胺[1]。但是在双酚芴钾盐和N-甲基-4-硝基酞酰亚胺发生亲核取代生成双醚酞酰亚胺的产品非常少,一方面合成方案还有待于改进,另一方面是产品的后处理应找到合适的方法。     

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。     

芴空气气相催化氧化制备9-芴酮的研究

本文阐述了一种由芴空气气相催化氧化制备9-芴酮的方法,该化合物应用于合成高耐热功能高分子材料,氧化催化剂的主要成分是V2O5和TiO2,本文采用的原料为工业芴,芴的转化率为98%,选择性为99%,本文同时考察了反应温度、空速、催化剂负荷对芴转化率及9-芴酮选择性的影响。     

The synthesis,photophysical properties and fluoride anion recognition of a novel branched organoboron compound

A novel two-branched organoboron compound, N,N-bis(7-dimesitylboryl-9,9-diethyl-9H-fluorene-2-yl)aniline, containing a phenylamino group as a π-electron donor, fluorene groups as π-bridges and dimesitylboryl groups as electron acceptors, was synthesized and its photophysical properties in various solvents as well as its fluoride anion recognition properties were investigated. The synthesised compound exhibited strong fluorescence in all solvents with the fluorescence changing from blue to orange on going from solvents of low polarity to those of high polarity. The compound was able to recognize fluoride anions in high sensitivity owing to strong interactions between boron atoms and fluoride anions.     

Diazobenzo[a]fluorene derivatives as visible photosensitizers for free radical polymerization

Several benzophenazine dyes containing a diazobenzo[a]fluorene moiety have been synthesized and characterized by ¹H NMR spectroscopy and mass spectrometry (CI MS). The spectroscopic and electrochemical properties of these dyes were examined. These compounds were evaluated as potential light absorbing chromophores for free radical polymerization. The results are discussed on the basis of the free energy change for electron transfer from the diazobenzo[a]fluorene dyes to the electron donors/acceptors. The kinetic studies of the photoinitiated polymerization of trimethylolpropane triacrylate (TMPTA) using electron donors, such as phenylthioacetic acid, phenoxyacetic acid, N-phenylglycine and ethyl 4-N,N-dimethylaminobenzoate, and electron acceptors, such as 1-methoxy-4-phenylpyridinium tetrafluoroborate and 1-ethoxy-2-methylpyridinium hexafluorophosphate, have shown that these dyes are efficient photoinitiators for free radical polymerization in visible light. The heavy atoms present in the chemical structure may lead to excited triplet states within the dye facilitating electron transfer from these states.     

pH-Sensitive performance of dextran–poly(acrylic acid) copolymer and its application in controlled in vitro release of ibuprofen

Dextran–poly(acrylic acid) copolymers (D-A) are prepared through copolymerizing of acrylic acid (AA) with dextran. Their structural properties and performances are characterized using various methods. The results indicate that the carboxyl groups of poly(acrylic acid) strongly interact with the proton acceptors of glucose units in dextran, and the effects of AA/dextran molar ratio on the pH sensitivity of obtained copolymers are remarkable. The D-A copolymer shows a smart pH response, specifically, shrinkage in a low pH medium and swelling at high pH. The potential application of D-A copolymer as a drug delivery matrix is explored using ibuprofen as a model drug.     

Theoretical Electronic Structure and Properties of Alternating Fluorene–Acceptor Conjugated Copolymers and Their Model Compounds

The theoretical geometries and electronic properties of fluorene (F) based alternating donor–acceptor conjugated copolymers and their model compounds were studied by the density function theory (DFT) at the B3LYP level with 6–31G or 6–31G** basis set. The acceptors investigated in this study include thiazole (TZ), thiadiazole (TD), thienopyrazine (TP), thienothiadiazole (TT), thiadiazolothienopyrazine (TTP), quinoxaline (Q), benzothiadiazole (BT), pyrazinoquinoxaline (PQ), thiadiazoloquinoxaline (TQ), and benzobisthiathiadiazole (BB). The torsional angle, bridge bond length, bond length alternation, and intramolecular charge transfer were simulated and correlated with the electronic properties, i.e., HOMO, LUMO level, and band gap. The geometries of fluorene-based donor–acceptor alternating copolymers and their model compounds are significantly affected by the structure of acceptors, particularly the ring size on the backbone. The electronic properties of the polymers and their model compounds are well correlated with the acceptor strength, coplanarity of the backbone, and intramolecular charge transfer. The theoretical study suggests that the electronic properties of alternating fluorene–acceptor conjugated copolymers could be tuned by the geometries or acceptor strength. Hence, these proposed copolymers could have potential applications as light-emitting diodes (LEDs), transparent conductor, or photovoltaic devices.     

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.     

含双酚芴三元共聚聚砜的合成与性能

以双酚芴（BHPF）、双酚A（BPA）、4，4⁃二氯二苯砜（DCS）为原料，采用亲核取代法合成了不同BHPF含量的三元共聚聚砜，研究了反应溶剂、反应时间和成盐剂等对聚合反应的影响，并采用凝胶渗透色谱仪（GPC）、红外光谱仪（FTIR）和差示扫描量热仪（DSC）等对含BHPF三元共聚聚砜的结构和性能进行了表征。结果表明，选用N⁃甲基吡咯烷酮（NMP）为反应溶剂，碳酸钾为成盐剂，设定反应时间为4 h时，可制备得到数均分子量（M_n）>2×10⁴的三元共聚物，且随着BHPF含量的增加，聚合物的玻璃化转变温度（T_g）逐渐提高，为209~254 ℃，主链分解温度>510 ℃，表现出了优异的耐热性能。当BHPF含量为80 %（摩尔分数）时，材料的T_g为254 ℃，可见光范围内透光率为84 %，可满足飞机高马赫数下的耐温需求，为高耐热透明材料的应用奠定了基础。     

Synthesis of a new conjugated polymer based on benzimidazole and its sensory properties using the fluorescence‐quenching effect

A new anionic conjugated polymer containing a fluorene group in the main chain was designed and synthesized from poly(2,7‐(9,9′‐dihexylfluorene)‐5,5′‐bibenzimidazole) (PFBI). The polymer showed strong blue emission with high quantum efficiency (0.64) at 450 nm in MeOH and the dramatic quenching effect by Methyl Viologen (MV²⁺). The fluorescence‐quenching effect results from the weak complex formation between an anionic polymer and electron acceptors such as bipyridinium derivatives. The linear Stern–Volmer constant (K_sv) was 3.7×10⁵ M^?1 for MV²⁺. The newly synthesized polymer is expected to show the applicability for biological and chemical sensors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 900–904, 2004     

芴液晶的研究进展

介绍了近年来芴液晶的研究进展,包括以芴酮(醇)及9位取代芴为核心的液晶化合物,阐述了这类化合物的结构与液晶性质及光电性质之间的关系。该类化合物在光电发光材料、有机太阳能电池材料等领域有广泛的应用前景。