测镉新试剂2—羧基—4—溴苯重氮氨基偶氮苯的合成及该类试剂结构与分析性能

合成了新的测镉试剂２－羧基－４－溴苯重氮氨基偶氮苯并研究了在ＴｒｉｔｏｎＸ－１００存在下与镉的显色反应。把该显色反应结果与同类试剂邻羧基苯重氮氨基偶氮苯、间羧基苯重氮氨基偶氮苯、对羧基苯重氮氨基偶氮苯、２，４－二溴－６－羧基苯重氮氨基偶氮苯和２，６－二溴－４－羧基苯重氮氨基偶氮苯与镉的显色反应进行了比较，从而讨论了试剂结构与分析性能之间的关系。     

对苯磺酰烷基胺偶氮—2—萘酚系聚丙烯纤维用橙色染料的合成及应用

本文以对氨基苯磺酰烷基胺重氮盐与2－萘酚偶合，分别制得了对苯磺酰正丁胺偶氮－2－萘酚、对苯磺酰正辛胺偶－2－萘酚、对苯磺酰正十二胺偶氮－2－萘酚和对苯磺酰正十八胺偶氮－2－萘酚系聚丙烯纤维用橙色染料，其熔点分别为187．6℃、165．9℃、138．0℃和108．1℃；热分解点309．5℃、302．5℃、262．1℃和215．8℃；最大吸收波长分别为480．2nm、480．2nm、480．0nm和480．0nm。在染色条件下，经过120分钟染色，四只染料在聚丙烯纤维上的上染率分别为51．1％、54．0％、55．9％和57．9％。     

测镉新试剂2－羧基－4－溴苯重氮氨基偶氮苯的合成及该类试剂结构与分析性能关系的研究

合成了新的测镉试剂２－羧基－４－溴苯重氮氨基偶氯苯并研究了在ＴｒｉｔｏｎＸ－１００存在下与镉的显色反应。把该显色反应结果与同类试剂邻羧基苯重氮氨基偶氮苯、间羧基苯重氮氨基偶氮苯、对羧基苯重氮氨基偶氮苯、２，４－二溴－６－羧基苯重氮氨基偶氮苯和２，６－二溴－４－羧基苯重氮氨基偶氮苯与镉的显色反应进行了比较，从而讨论了试剂结构与分析性能之间的关系。     

锌粉-卤化铵还原体系用于N，N’-二苯肼的合成

采用Zn—NH4X（X=F、Cl、Br、I）还原体系,从偶氮苯制备N,N’-二苯肼。讨论了偶氮苯与锌粉物质的量比,卤化铵饱和溶液的用量对反应的影响。其中Zn—NH4Cl还原体系的优化反应条件为：偶氮苯与锌的摩尔比为1：5（偶氮苯2．5mmol）,饱和氯化铵溶液1．5mL,反应时间12min,产率92．62％。     

锌-醋酸铵还原体系用于对称二苯肼合成的研究

采用Zn-NH4OOCCH3还原体系，从偶氮苯制备氢化偶氮苯，最佳反应条件为：偶氮苯与锌的摩尔比为1：1.5，偶氮苯用量为2.5mmol时，饱和醋酸铵溶液1.0ml，反应温度25℃，反应时间9min，产率93%.     

导电偶氮苯共轭聚合物的合成及性能研究

采用过硼酸钠氧化4,4′-二氨基联苯合成了主链含偶氮苯的共轭聚合物。通过傅里叶变换红外光谱、拉曼光谱、紫外-可见吸收光谱、差示扫描量热仪、四探针测试仪对偶氮苯共轭聚合物的结构和性能进行了研究。结果表明,得到的偶氮苯共轭聚合物数均相对分子质量(Mn)为4482,其玻璃化转变温度(Tg)为186℃,并在热分析测试中发现共轭聚合物主链顺式构型偶氮苯单元;盐酸掺杂的偶氮苯共轭聚合物电导率为8.7×10-5 S/cm,碘掺杂的偶氮苯共轭聚合物电导率为2.65×10-4 S/cm,钠-萘掺杂的偶氮苯共轭聚合物导电率为1.92×10-4 S/cm,偶氮苯共轭聚合物经365nm(3mW/cm2)紫外光照射后,偶氮苯共轭聚合物的电导率扩大一个数量级,换用473nm(20mW/cm2)可见光光照后,其电导率发生回复,表明偶氮苯共轭聚合物具有光调制导电特性。     

氧化偶氮苯类化合物合成研究进展

氧化偶氮苯化合物作为一类有机化工原料和中间体在染料、指示剂及液晶材料等方面具有重要的应用。工业上常采用葡萄糖等还原剂在碱性条件下还原芳香硝基化合物来制备氧化偶氮苯化合物,但该方法存在环境不友好的问题。简述了氧化偶氮苯化合物的发展现状,介绍了芳香硝基化合物还原和芳香氨基化合物氧化两条反应路线制备氧化偶氮苯化合物的相关研究,分析了两条合成路线的反应机理,讨论了催化体系和反应条件对选择性制备氧化偶氮苯的影响因素,总结了各种催化体系的优缺点,指出氧化偶氮苯合成方法应进一步发展高效、廉价的催化体系,发展无溶剂或以离子液体为溶剂的合成方法和以光电等新能源驱动反应的合成方法,以实现氧化偶氮苯合成反应体系更加高效、绿色、经济和简便。     

对氨基偶氮苯盐酸盐工艺改进

对氨基偶氮苯盐酸盐工艺改进李萌（陕西渭南市染化厂７１４０００）对氨基偶氮苯盐酸盐是我厂于１９９１年开发出的一个中间体产品，呈浅兰色结晶体，熔点１２６～１２８℃，沸点３６０℃，微溶于水，溶于乙醚、苯和油类，与氨水共热则有棕色对氨基偶氮苯结晶沉淀。该产品...     

超声辐射合成3，3’-偶氮苯二甲酰氯

以3,3’-偶氮苯二甲酸为原料,氯化亚砜为酰基化剂,超声辐射快速合成3,3’-偶氮苯二甲酰氯。较佳工艺条件为：超声功率250W,3,3’-偶氮苯二甲酸1．5g,氯化亚砜30mL,反应温度80℃,反应时间4小时,收率达95．3％。标题化合物结构经红外光谱、核磁共振和元素分析得到确认。     

偶氮苯改性聚乙烯醇的研究

通过三聚氯氰的氯原子和聚乙烯醇的羟基之间脱氯化氢的反应,用含有2个偶氮苯的三聚氯氰衍生物改性聚乙烯醇（PVA）1788。红外光谱和核磁共振分析表明,在二氧六环和水混合溶剂中可以将偶氮苯成功接枝到PVA上,PVA中约每12个羟基就有1个发生反应。含有偶氮苯的PVA可以溶解在水和二甲亚砜中。其紫外可见吸收光谱与偶氮苯相似,并表现出偶氮苯的典型光致异构现象。     

Fabrication of surface‐relief gratings on an azobenzene‐containing epoxy‐based polymer film using atomic force microscopy

Many studies have been reported on the photo‐fabrication of surface‐relief gratings (SRGs) in azo‐polymer films using the interference of two laser beams of appropriate polarization. However, there are few reports in the literature concerning the electro‐fabrication of SRGs on such types of polymer films. The goal of the work reported was the electro‐patterning of an azobenzene‐containing epoxy thermoplastic film. An epoxy‐based polymer functionalized with an azo‐chromophore was synthesized and characterized using thermal analysis. The reversible optical storage properties and photo‐induced dichroism were studied. SRGs were fabricated on a film of the synthesized azobenzene‐containing polymer using contact mode current‐sensing atomic force microscopy which locally applied an electric field that aligned the azobenzene moieties. The anisotropic mass transport of the azo‐polymer film was observed after applying an electric field. Additionally, the effect of the relief formation in the polymeric film surface was investigated by means of atomic force microscopy and electrostatic force microscopy. Copyright © 2010 Society of Chemical Industry     

Chromophore concentration effect on holographic grating formation efficiency in novel azobenzene‐functionalized polymers

Optically active photochromic poly(amideimide)s containing azobenzene side groups in the repeating unit were prepared. The polymers were designed and synthesized specifically for this work in order to evaluate chromophore concentration effect on holographic grating recording. The poly(amideimide)s with mono‐ and bis‐azobenzene moieties were obtained via direct high temperature polycondensation and compared with respect to their ability of diffraction grating formation due to the light‐induced optical anisotropy effects. Holographic gratings were fabricated in polymer films upon exposure to an interference pattern of two polarized Ar⁺ laser beams at 514.5 nm wavelength. Different geometries of laser beams polarization were applied. It should be emphasized that although the azobenzene moieties are rigidly connected to the polymers backbone, some of polymers exhibited the unusually high light diffraction efficiency of around 40%. The created surface relief gratings (SRGs) were successfully observed using the atomic force microscopy (AFM). AFM images show regularly defined and aligned grating structures. It should be stressed that the SRGs with maximum of relief height up to 260 nm in polyimide derivatives with side azobenzene group were observed for the first time. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of photoactive poly(arylene ether sulfone)s containing azobenzene moieties in their main chains

A series of azobenzene functionalized poly(arylene ether sulfone)s (azo-PAESs) has been synthesized via nucleophilic aromatic substitution polycondensation, and azobenzene chromophores could be introduced into the polymer main chains by copolymerization from azo-monomers. These main chain type azo-PAESs have high glass transition temperatures and good thermal stability. Exposed to an interference pattern laser beam, spin-coated films of the azo-PAESs can form clear and stable surface relief gratings (SRGs). These SRGs show increased thermal stabilities with the content of azo moieties and cannot be fully removed until the temperature increases to 300 °C for azo-PAESs with a content of azo segments above 50%.     

Preparation and optical performance of chiral polymers having azobenzene segments

A series of monomeric azobenzene derivatives of 6‐(4‐nitro‐4′‐oxy‐azobenzene acrylate with carbon numbers of 6 and 11, and the chiral monomer of bornyl 4‐(6‐acryloyloxyhexyloxy)‐phenyl‐4′‐benzoate were synthesized. Chiral polymers having bornyl group end‐capped pendants with azobenzene‐derived segments were prepared. Molecular structures and polymer compositions were confirmed by using ¹H‐NMR, elemental analysis, FTIR, and UV–vis analyzers. Thermodynamic properties of both monomers and polymers were investigated. Specific rotations of chiral monomers and polymers were estimated by using an automatic digital polarimeter. Liquid crystalline textures of monomers and polymers were analyzed by using a polarizing optical microscope and confirmed by a small‐angle X‐ray analyzer. The optical reflection characteristics of composite cells with chiral nematic liquid crystal and various amounts of azobenzene derivatives were evaluated by using a UV–vis spectrophotometer. The reliability and stability of the composite cells with E48/S811 and azobenzene derivatives were studied. The photoisomerization of the chiral polymer film was investigated by using SEM and AFM analyzers. It was found that the UV irradiation of a laser spot caused the shrinkage of polymer film due to the photoisomerization of azobenzene segments. The contraction of the polymer film can be recovered by heat treatment. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3693–3704, 2004     

含偶氮苯基的侧链液晶高分子的研究进展

综述了含偶氮苯基的侧链液晶高分子的最新研究进展,对偶氮类液晶高分子的各种制备方法和表征进行了总结和评价,对其在光学材料、液相色谱等方面的应用也作了介绍。     

Optical properties of some new azo photoisomerizable bismaleimide derivatives

Novel polythioetherimides bearing azobenzene moieties were synthesized from azobismaleimides and bis-2-mercaptoethylether. Kinetics of trans-cis photoisomerization and of thermal conversion of cis to trans isomeric forms were investigated in both polymer solution and poly(methyl methacrylate) doped films using electronic absorption spectroscopy. Thermal recovery kinetics is well described by a two-exponential relation both in solution and polymer matrix, while that of low molecular weight azobismaleimide fit a first-order equation. The photoinduced cis-trans isomerization by visible light of azobenzene chromophores was examined in solution and in polymer films. The rate of photoinduced recovery was very high for azobismaleimides.     

A rapid photomechanical switching polymer blend system composed of azobenzene-carrying poly(vinylether) and poly(carbonate)

A new material with photomechanical switching ability was developed. The material is a binary polymer blend composed of a poly(vinylether) having azobenzene moiety in the side chain and a polycarbonate as a matrix. Upon switching UV-irradiation on and off, the developed polymer blend showed deformation that was both rapid and reversible. This observed photomechanical effect is attributed to a reversible modulus change in the polymer blend, arising from an UV-controlled isomerization of the azobenzene moiety, causing a switching behavior between its highly aggregated and dissociated states. These two states are the physical crosslinking and decrosslinking of the polymer chains.     

Ionomeric polyurethanes of pyridinium type with side azobenzene groups

New polyurethane cationomers synthesized by a two‐step substitution postreaction of urethane hydrogen atoms with nitroazobenzene groups were studied. As a starting polymer, a polyurethane based on poly(tetramethylene oxide)diol, isophorone diisocyanate, and 2,6‐bis(hydroximethyl)pyridine was used. After a preliminary metalation of the above polymer with natrium hydride, by reaction of polyurethane N‐sodate with 4‐nitro‐4′(β–iodoethylurethane)azobenzene, chromophoric groups between 2.85 and 10.53 wt % could be incorporated instead of hydrogen. Such polymers partially functionalized with azobenzene and further quaternized with methyl iodide led to the formation of pyridinium polyurethane cationomers N‐modified with nitroazo groups. The photosensible properties of the azobenzene chromophore in a polymer solution and film state indicated important differences in their photoresponse. In the polymer solution, the trans–cis photoisomerization of the chromophore is accompanied by an irreversible photobleaching effect, while under the same UV irradiation conditions, the ionomeric films exhibited an enhanced photostability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1240–1247, 2002     

Azobenzene isomerization in polymer co-crystalline phases

Three different co-crystalline phases of syndiotactic polystyrene (s-PS) with azobenzene have been prepared and structurally characterized. The triclinic δ-clathrate phase is characterized by a styrene-monomeric-unit/guest ratio (SU/G) equal to 8/1 while the δ-intercalate phase is characterized by SU/lG = 4/1. The orthorhombic ε-clathrate phase allows stacking of a variable number of guest molecules per monomer unit with SU/G ≥ 9/1. Isomerization reactions of the azobenzene guest molecules (both photo-induced trans → cis and spontaneous cis → trans) have been studied by UV–Visible and FTIR measurements. Repeated isomerization cycles produce progressive desorption from the polymer film of azobenzene molecules being simply dissolved in s-PS amorphous phases, while poorly affect the content of azobenzene molecules being guest of s-PS co-crystalline phases. Polarized FTIR spectra of axially oriented films indicate that isomerizations occur without expulsion of azobenzene guest molecules from the polymer co-crystalline phases. The whole set of data indicate that films exhibiting co-crystalline phases of azobenzene with s-PS are suitable for producing self-erasing photo-isomerization patterns with molecular size marks.     

Synthesis of photoisomeric azobenzene monomers and model compound effect on electric–optical properties in PDLC films

A series of azobenzene monomers and related model compounds with various side‐chain lengths were synthesized. The electrooptical properties of a polymer‐dispersed liquid crystal (PDLC) were verified by side‐chain methoxy azobenzene in various chain lengths (n = 3, 6, 11). The properties under various voltages were measured and the effect of extra voltage on the transmittance of PDLC was researched as well. The experiment demonstrated the validity of employing these side chain methoxy azobenzene materials in electrooptical devices. The azobenzene model compound showed better electric–optical and thermal–optical properties, having a higher contrast ratio (CR = 689) and a lower saturation voltage (4.7 V/μm). All the azobenzene molecules can be photoisomerized through UV light irradiation, following the mechanism of isomerization. The reversible photo and heat isomerization property was studied. The cis‐azobenzene that was transformed from the trans‐azobenzene irradiated by UV light can decrease the clearing point of the liquid crystal phase. We used this unique characteristic to record image patterns and it worked successfully. We synthesized the azobenzene monomers can stabilize the PDLC and their relative model compounds with various alkyl chain lengths even got better electric–optical effects. We found that azobenzene monomer shows different behaviors in the electric–optical property from its relative model compound. The difference between the systems were explained using a proposed model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 721–732, 2005