Gemini对PVA分散螺吡喃有机凝胶薄膜光致变色行为的调控

通过共溶剂-乳化-溶剂挥发法制备了聚乙烯醇(PVA)分散螺吡喃(SP)光致变色有机凝胶薄膜(PDPGSP),采用双子型表面活性剂六亚甲基-1,6-双十二烷基二甲基溴化铵(Gemini)调控聚合物/有机凝胶界面相互作用,系统研究了薄膜光致变色行为、褪色行为、微观结构形貌、力学性能及耐疲劳性能.结果表明,PDPG-SP薄膜表现出良好的光致变色行为与类溶液的褪色行为,SP在薄膜中褪色速率与聚丙二醇(PPG)溶液相近;薄膜具有优异的力学性能,其弹性模量与拉伸强度分别高达~547和~23.5 MPa;经过10次变色-褪色循环后,薄膜最大吸收波长处吸光度A衰减了约35%,相比以PVA1为表面活性剂(衰减约53%),耐疲劳性明显提升.Gemini有序聚集过程中头基分离力的有效阻抑,抑制了PVA/有机凝胶界面对SP的锚定,使更多SP分子分布于自由异构的有机凝胶微环境,提高薄膜褪色速率,同时可逆异构分子数量的增加,使薄膜耐疲劳性提高.     

PEDOT基光子晶体的制备及其电致变色性能研究

采用改进的Stöber法合成了单分散SiO₂微球, 通过垂直沉积组装成蛋白石结构光子晶体. 再使用电化学法在组装的SiO₂微球表面生成聚(3,4-乙撑二氧噻吩)(PEDOT), 得到核-壳结构的SiO₂@PEDOT光子晶体复合膜. 测试了SiO₂@PEDOT光子晶体薄膜的反射光谱、循环伏安曲线、多电位紫外反射光谱、对比度及响应时间等光学、电化学及电致变色性能. 结果表明, 该光子晶体薄膜在变色时颜色亮丽, 其色差值(26.82)比纯PEDOT薄膜(18.07)提高很多, 并且最大对比度可达39.8%, 高于纯PEDOT薄膜的27.4%, 同时响应时间变快. 此实验结果说明将光子晶体结构引入导电聚合物中, 能够提高其电致变色性能.     

SiO_2@PANI光子晶体的制备及电致变色性能研究

应用Stber法合成单分散SiO2微球,通过垂直沉积自组装光子晶体,由电化学法在所组装的SiO2微球表面生成聚苯胺(PANI),得到了核-壳结构SiO2@PANI光子晶体薄膜.测试了SiO2@PANI光子晶体薄膜的循环伏安曲线、多电位紫外吸收光谱、对比度、响应时间等电致变色性能,结果表明,该光子晶体薄膜在变色时颜色亮丽,其最大对比度可达77%,远高于单纯PANI薄膜的43%,同时响应时间变快.初步实验结果说明将光子晶体结构引入导电聚合物中,能够提高其电致变色性能.     

紫精类化合物分子聚集体材料的界面组装

紫精类化合物具有良好的电化学活性,并且在发生氧化还原反应时伴有颜色的变化,在膜修饰电极、电致变色材料和分子器件的研制等方面受到广泛的关注。紫精中的烷基链非常易于进行化学修饰,因而比较适合于通过自下而上的分子自组装技术制备多功能的分子和纳米材料。本文综述了利用Langmuir-Blodgett法、自组装法和层层组装法制备紫精分子聚集体材料的研究进展,并讨论了分子聚集体薄膜中紫精的结构、电致变色、电化学氧化还原特性及其在研制超分子器件方面的应用。     

壳聚糖辅助制备WO_3薄膜材料及其电致变色性能

以壳聚糖(CS)为辅助材料,利用层层自组装方法(LbL)制备了WO3复合薄膜材料(CS/WO3).采用紫外-可见吸收光谱(UV-Vis)、扫描电子显微镜(SEM)和循环伏安扫描(CV)等手段对CS/WO3纳米复合材料的形貌和电化学性能进行了表征.利用电化学和UV-Vis联机技术研究了复合材料的电致变色性能.结果表明,该复合材料呈现出从无色到蓝色的颜色调变,其光反差可达48.0%,着色效率为58.5cm2/C,着色与褪色时间分别为9.5和1.8s.     

可注射性骨修复材料不饱和聚磷酸酯的光引发交联聚合

通过凝胶含量的测定,研究了紫外光引发不饱和聚磷酸酯(UPPE)与 N-乙烯基吡咯烷酮的共聚交联反应.结果表明:加入光引发剂能够显著增加凝胶含量,安息香乙醚(BE),安息香(BN),2,2-二乙氧基苯乙酮的引发活性较高.光引发剂浓度较低时,增加光引发剂的含量能够显著提高单位时间内的凝胶生成率,但含量过大反而降低凝胶生成率.BN、BE的适宜浓度分别为2.4E^-5(mol/g UPPE)及0.6E^-5(mol/g UPPE).光照较短时间内,UPPE分子量为5960 g/mol的体系具有最高的凝胶生成率,但由于粘度的影响,光照2 min后其凝胶生成率低于UPPE分子量为4040 g/mol的体系.表层对紫外光的吸收降低了光能量,导致深层交联聚合反应速度降低,1.5 mm厚试样通过延长曝光时间,凝胶含量可与1.0 mm厚试样接近,6.0 mm试样曝光24 min后底层仍不能固化.     

紫精化合物的合成与应用研究进展

紫精化合物（viologens）是一类具有独特变色性质的缺电子体阳离子化合物，在变色材料、超分子器件和有机电池等方面有着潜在的应用前景。可通过取代反应设计合成具有不同取代基的紫精，实现性能调控。本文对近年来紫精化合物的合成方法与应用研究进展进行了综述，重点介绍了其在变色、发光等性能方面的潜在应用。     

聚苯胺电致变色薄膜在不同颜色区间的电化学循环稳定性研究

本文采用电位阶跃和循环伏安法结合紫外可见光光度法研究了聚苯胺薄膜的电致变色性质. 聚苯胺薄膜颜色多变,颜色在浅黄色到绿色再到蓝色之间变化,本文研究在不同的颜色变化区间内聚苯胺薄膜的电化学循环稳定性. 研究结果表明,薄膜在黄色到蓝色(0.4 V ~ 1.2 V)以及绿色到蓝色(0.8 V ~ 1.2 V)区间变化时,电致变色循环性能较差,而在黄色和绿色(0.4 V ~ 0.8 V)之间变化时循环稳定性能良好,着色时间为4.5 s,着色效率高达159.48 cm²·C^-1.     

盘状多酸P_5W_(30)/阳离子聚电解质/氧化石墨烯杂化多层膜的电致变色性能

为了提高薄膜[PEI/P_5W_(30)]_(30)的电致变色性能,将具有大的二维尺寸和良好导电性的氧化石墨烯引入该薄膜中。通过层层自组装(LBL)技术构筑了基于盘状多酸K12.5Nal.5[Na P_5W_(30)O_(110)]·15H_2O(P_5W_(30))、氧化石墨烯(GO)的复合薄膜[PEI/P_5W_(30)/PEI/GO]_(30)(PEI:聚乙烯亚胺),并利用UV-Vis光谱对薄膜的组成及增长进行监测;通过原子力显微镜对薄膜的表面形貌进行考察,利用循环伏安法对薄膜电化学氧化还原性质进行研究;薄膜在外加氧化还原电位下呈现出无色/蓝色的可逆变化,电致变色响应时间在10 s以内;此外,薄膜在阶跃电位0.75 V/-0.75 V下循环150次,电致变色性能没有明显减弱,体现了薄膜良好的电致变色可逆性。氧化石墨烯的引入使薄膜[PEI/P_5W_(30)/PEI/GO]_(30)呈现出响应速度快、抗电疲劳强的电致变色性能,将在电致变色器件领域有广阔的应用前景。     

紫精-普鲁士蓝凝胶电致变色器件的制备

合成了醛基功能化的紫精,1,1′-二醛己基-4,4′-联吡啶,通过与聚乙烯醇的缩醛反应将紫精固定到凝胶电解质中,对电极用电沉积法沉积普鲁士蓝,制备了新型凝胶型电致变色器件。这种凝胶电致变色器件避免了电解质泄露的风险并拓宽了电致变色器件的应用范围。采用1 HNMR对分子结构进行了表征,通过紫外-可见分光光度计研究了器件的电致变色性能及其影响因素。结果表明:采用将紫精通过共价键并入凝胶的方法,制备的器件在±2V的工作电压下具有47%的对比度,着色时间2.8s,褪色时间3.3s,并且具有良好的循环稳定性。     

Development of Photochromic Coatings on Polycarbonate

New photochromic materials based on heteropolyoxometallates (HPOM) incorporated into a hybrid organic-inorganic binder were prepared and coated onto polycarbonate (PC) substrates. The hybrid binder was formed through the controlled hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) by the sol–gel technique. The photochromic behavior of the materials was investigated by using ultraviolet-visible (UV-Vis) absorption spectroscopy and color index values. The results indicated that the films were reduced photochemically to yield a blue species under UV irradiation, with the film color changing to deep blue with increasing time, and HPOM and BPA content. The photosensitivity of several films with molybdenum HPOM showed faster coloration and much slower bleaching than the tungsten HPOM. A photochromic mechanism involving electron transfer between the GPTMS matrix with BPA, and PWO is proposed. After UV irradiation, the O–H and bonds decomposed gradually and W^{6 +} was reduced gradually with increasing time. The photochromic coatings on PC substrate showed reversible transmittance change before and after UV irradiation, making then efficient light protectors under UV irradiation.     

Photochromic and photomechanical ionene elastomer containing poly(tetrahydrofuran) segments and viologen units

Elastomeric polymer consisting of poly(oxytetramethylene) segments and viologen units (PTV) was synthesized by the reaction of dicationic living poly(tetrahydrofuran) with 4,4′-bipyridine at ?70°C. The chloride or bromide ion was introduced as the counter anion into the viologen groups of PTV by the treatment of the reaction mixture with aqueous sodium chloride or bromide, respectively. The solid film of PTV having chloride inon showed photochromism, i.e., color change by light irradiation, via photoreduction of the violegen groups. In contrast. PTV of bromide counter anion required a small amount of poly(N-vinyl-2-pyrrolidone) to undergo the photochromic reaction. The irradiation of light also affected the stress relaxation of the polymers, namely PTV showed photomechanical behavior. This phenomenon is considered to be induced by the decrease of total number of ionic charges of PTV by photo-reduction of the viologen groups followed by the change of a state of ionic clustering in the polymer matrix.     

Polymer micelles as building blocks for the incorporation of azobenzene: enhancing the photochromic properties in layer-by-layer films

We described the use of block copolymer micelles as building blocks for the incorporation of water-insoluble photochromic species of azobenzene and the fabrication of multilayer films by alternating the deposition of the block copolymer micelles of poly(styrene-b-acrylic acid), incorporating azobenzene and poly(diallyl-dimethylammonium chloride). The azobenzene incorporated into the block copolymer micelles can undergo a reversible photoisomerization under the irradiation of UV and visible light sources. An interesting finding is that the photoisomerization of the azobenzene in the multilayer film is faster than it is in its normal solid film, but very similar to that in its diluted solution. Furthermore, the amount of azobenzene incorporated into the micelles can influence the photoisomerization rates in the films. Therefore, we expect that the block copolymer micelles may provide a proper microenvironment for the photoisomerization of azobenzene and the as-prepared polyelectrolyte/block copolymer micelle thin films will be useful for photoswitching materials.     

Structure, photochromic, and electrochemical properties of dioctadecylamine/H3PMo12(O)40 Langmuir-Blodgett film

We used the Langmuir-Blodgett (LB) technique to construct a well-defined and structure-controllable photochromic material-a highly ordered multilayer film composed of dioctadecylamine and 12-molybdophosphoric acid (PMo12). We identified well-ordered lamellar structures using X-ray diffraction, polarized IR, and Raman spectra, and we determined a packing model of the two components in the LB film. We found the Keggin structure and fundamental features of the PMo12 ion to be maintained in the hybrid film. This hybrid LB film displayed photochromic properties upon UV light irradiation and we observed the following process from first-order kinetics. The photochromism exhibited the ability to switch between colorless and blue. A fading process occurred when the film was exposed to ambient air or O2 in the dark. During the color change, the packing structure of the film was well maintained. We also examined the electrochemical behavior of the hybrid LB film by cyclic voltammetry in detail and we propose different kinetic mechanisms for the film before and after irradiation.     

SYNTHESIS AND PHOTOCHROMISM OF ACRYLIC ESTER COPOLYMERS BEARING PENDANT VIOLOGEN GROUPS

A series of acrylic ester copolymers with viologen group as pendant were synthesizedthrough the reaction of MMA-EBA (Ethenyl bromoacetate) copolymer with 4-(4'-pyridyl)-N-alkyl (or arylalkyl) pyridiniums. These viologen copolymers can exchange their anionwith NH_4PF_6 in methanol to improve their solubility in organic solvents such as DMFand acetone. Compared with the corresponding low molecular viologens, these viologencopolymers have relatively lower color development rate under UV light and fade fasterin air due to less affinity to photo-reductant and deficiency of association between theircation radicals. Their photofatigue resistant ability is also slightly better than that of lowmolecular vinlogens.     

UV-light and visible-light photochromism of inorganic–organic multilayer films based on polyoxometalate and poly(acrylamide)

Novel UV-light and visible-light photochromic inorganic–organic multilayers composed of polyoxometalates (phosphomolybdic acid (PMoA)) and poly(acrylamide) (PAM) were prepared by the layer-by-layer (LbL) self-assembly method. The grown process, composition, surface topography, and photochromic properties and mechanism of the multilayer films were investigated by ultraviolet–visible (UV–vis) spectra, Fourier transform infrared spectra (FT-IR), atomic force microscopy (AFM), electron resonance spectra (ESR), and X-ray photoelectron spectra (XPS). Irradiation with UV-light or visible-light, the transparent films changed from colorless to blue and showed reversible photochromism. PMoA/PAM LbL films had higher photochromic efficiency under UV-light irradiation than visible-light irradiation. The bleaching process occurred when the films were in contact with O₂ in the dark or heated in air. The photochromic process of PMoA/PAM LbL film was in accordance with radical mechanism.     

Diacetylene-containing polymers,II. Polyesters and polyurethanes containing m,m′-butadiynylenedibenzyl groups

Diacetylene-containing polyesters and polyurethanes were prepared by the reaction of m,m-butadiynylenedibenzyl alcohol with isophthaloyl chloride, sebacoyl chloride, hexamethylene diisocyanate and 2,4-tolylene diisocyanate. Their thermal behavior was studied by optical microscope and differential scanning calorimetry (DSC). The polyesters were crystalline. The polyurethane prepared from hexamethylene diisocyanate and polyphthalates crystallized on cooling from their melts. All turned a reddish brown color on heating at temperatures above 200°C, and prolonged heating led to a black resin, but thermal decomposition could not be avoided. Irradiation by γ-ray and UV light at room temperature deepened the color of the films, but the polymerization of the diacetylene groups was not appreciable. Simultaneous heating and irradiation was necessary to obtain transparent, amorphous, wine red colored films.     

Photocontrolled Intramolecular Charge/Energy Transfer and Fluorescence Switching of Tetraphenylethene‐Dithienylethene‐Perylenemonoimide Triad with Donor–Bridge–Acceptor Structure

Photochromic 1,2‐dithienylethene (DTE) derivatives with a high thermal stability and fatigue resistance are appealing for optical switching of fluorescence. Here, we introduce a donor–photochromic bridge–acceptor tetraphenylethene‐dithienylethene‐perylenemonoimide (TPE‐DTE‐PMI) triad, in which TPE acts as the electron donor, PMI as the electron acceptor, and DTE as the photochromic bridge. In this system, the localized and intramolecular charge transfer emission of TPE‐DTE‐PMI with various Stokes shifts have been observed due to the photoinduced intramolecular charge transfer in different solvents. Upon UV irradiation, the fluorescence quenching resulting from photochromic fluorescence resonance energy transfer in TPE‐DTE‐PMI has been demonstrated in solution and in solid films. The fluorescence on/off switching ratio in polymethylacrylate film exceeds 100, a value much higher than in polymethylmethacrylate film, thus indicating that the fluorescence switching is dependent on matrices.     

Effect of alkali metal ions on photochromic behavior of bisviologen-incorporated oligo-oxyethylene units

Two bisviologen derivatives, 1,11-bis(N-propyl-4,4'-bipyridinium)-3,6,9-trioxaundecane tetrakis-(hexafluorophosphate) (1) and 1,8-bis(N-propyl-4,4'-bipyridinium)-3,6-dioxaoctane tetrakis-(hexafluorophosphate) (2), each incorporating trioxaundecane and dioxaoctane groups between two viologen units, respectively, were prepared so that their photochromic behavior in the absence and the presence of alkali metal ions in a thin polymer film could be investigated. Photoirradiation of the films containing 1 and 2 caused color changes from pale yellow to blue, associated with the photoinduced reduction of the viologen units from the dication to the radical cation. The addition of alkali metal ions, especially, K+ and Na+, caused change in the spectra of the photoreduced viologen radical cation for 1 and 2, respectively, because of the increase in the fractional amplitude for the dimer component of the radical cation rather than the monomer one. This may be related to the guest-induced conformational change of 1 and 2, in which the alkali metal ion is surrounded by the oligo-oxyethylene unit of 1 and 2. The regulation in photochromic properties of viologen derivatives can be achieved by addition of alkali metal ions.     

Accelerating the thermal fading rate of photochromic naphthopyrans by pillar[5]arene-based conjugated macrocycle polymer

A new micro-spherical conjugated macrocycle polymer (P[5]-TFB-CMP) was prepared by the condensation reaction between dihydrazide functionalized pillar[5]arene and 1,3,5-triformylbenzene under ambient conditions. P[5]-TFB-CMP exhibits large surface area with excellent thermal stability and has been used as additive to prepare composite PMMA film of photochromic naphthopyrans. The results showed that the addition of P[5]-TFB-CMP could dramatically accelerate the thermal fading rate of the photochromic composite film by up to 12 times. This is a new strategy to overcome the drawback of the matrix effect.