螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

螺噁嗪光致变色反应机理研究进展

20世纪80年代中期以来, 关于螺噁嗪在光致变色过程中的光化学和光物理现象的研究非常活跃. 综述了近20年来对溶液中的螺噁嗪、晶体螺噁嗪以及固体介质中的螺噁嗪的光致变色机理研究结果, 同时介绍了实验研究方法和理论研究方法在螺噁嗪光致变色过程研究中的应用, 分析了取代基对光致变色性质的影响. 阐述了机理研究对新型螺噁嗪设计合成的重要指导意义.     

基于螺噁嗪的快速可逆力响应性聚合物的研究

机械力响应性聚合物的设计目前引起国内外广泛的关注,但力致变色聚合物中的力色团的设计仍然是巨大的挑战.本工作设计并合成了一种全新的螺噁嗪力色团结构,并将其引入以聚二甲基硅氧烷(PDMS)为基体的聚合成交联网络结构中.通过对螺噁嗪小分子溶液和聚合物的紫外光照射验证了螺噁嗪力色团结构在紫外光刺激下的响应性以及快速恢复性;拉伸和循环拉伸实验来验证聚合物优异的力致变色行为;从CIE图则更加直观地看到聚合物在拉伸过程中由无色变为红色而撤掉机械力瞬间变为蓝色并在短暂时间内恢复为无色.综上本文主要介绍了一种全新的力色团结构基于PDMS所制备出的柔性高分子材料,由于其优异的力致变色性能以及快速恢复性,在应力示警、柔性变色材料传感器方面都有一定的潜力.     

新型含螺噁嗪聚甲基丙烯酸甲酯微球的制备与光致变色性能

以甲基丙烯酸甲酯（MMA）为原料,螺噁嗪（SPO）为光致变色染料,经悬浮聚合法制备了光致变色微球（PMMA SPO）,其结构经红外光谱、扫描电镜和差热分析表征。研究了SPO浓度对微球转化率和环境温度对光致变色开环体热稳定性的影响。结果表明：在SPO的空间位阻效影响下,微球的玻璃化转变温度由82.4 ℃升高至85.3 ℃,随着SPO浓度下降,微球转化率由89%降低至15%,光致变色开环体的热稳定性随环境温度增大而增强,微球在淡粉色和黄绿色之间可逆转化20次以上未见明显的疲劳现象。     

N-乙基-9′-溴丁氧基螺噁嗪的合成及其化学改性PMMA的结构与光致变色性能

合成了分子结构中含活性C—Br键的N-乙基-9′-正溴丁氧基螺噁嗪(Br-SO),利用Br-SO分子结构中的化学基团C—Br与部分水解的聚甲基丙烯酸甲酯(hPMMA)反应制备含SO的PMMA高分子化合物(SO-hPMMA)。采用1 HNMR和IR对Br-SO结构进行了表征,研究了Br-SO、SO-hPMMA的光致变色性能及其影响因素。研究表明:Br-SO、SO-hPMMA均具有良好的光致变色性能,且SO-hPMMA的热稳定性明显高于Br-SO。     

含席夫碱基的螺噁嗪类光致变色化合物的合成及性质

设计合成了一系列含席夫碱基的螺噁嗪双功能光致变色材料4a~4d. 通过¹H NMR, ¹³C NMR, IR和HRMS对其结构进行了表征. 新化合物在几种有机溶剂中均表现出了良好的光致变色性. 研究了化合物在几种高分子膜中的光致变色性. 比较了化合物4b的开环体在两种不同溶剂, 即甲醇和二甲亚砜, 以及3种高分子介质, 即聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇缩丁醛(PVB)和聚乙烯醇(PVA)中的消色速率. 研究了化合物在甲醇、二甲亚砜、PMMA及PVB中的消色过程动力学, 根据化合物在溶液中和高分子介质中开环体消色过程的差别, 推测了存在两种动力学解释的原因. 研究结果显示, 化合物4d在PMMA膜中的耐疲劳度良好.     

含席夫碱基的螺吡喃双功能光致变色材料的合成及性质

设计合成了一系列含席夫碱基的螺吡喃双功能光致变色材料4a~4n. 通过1H NMR, IR和HRMS对其结构进行了表征. 研究了化合物在几种溶剂和PMMA膜中的光致变色性质, 研究了化合物4a在甲醇中, 以及化合物4a和4f在高分子介质聚甲基丙烯酸甲酯(PMMA)中的消色过程. 结果表明, 化合物4e在PMMA膜中光照后呈现出与其它化合物不同的颜色, 为罕见的绿色. 化合物4a在二氯甲烷溶液中有良好的荧光性能. 所合成的新型含席夫碱基的螺吡喃双功能光致变色材料在甲醇、二氯甲烷和环己烷溶液中及在PMMA膜中均表现出良好的光致变色性质.     

含肉桂酸酯基螺噁嗪的合成及性质研究

通过缩合法合成了含有肉桂酸酯基的双功能螺噁嗪类化合物,用红外光谱、核磁共振氢谱、碳谱和X射线单晶衍射对其结构进行了表征.紫外-可见光谱研究结果表明:当用400 W高压汞灯照射后化合物在有机溶剂以及高分子膜中都表现出了很好的可逆光致变色性.化合物也显示出了酸致变色性能.此外着重研究了化合物酸致变色荧光性能以及在150 W氙灯照射前后的荧光光谱.加入酸后和光照前后荧光光谱的改变使其有望作为荧光分子开关、非破坏性数据的读取存储介质材料.     

双功能螺吡喃螺噁嗪类光致变色化合物研究进展

光致变色材料在光学镜头、光学信息存储、光分子开关等方面具有广泛的应用.双功能光致变色材料的合成与应用研究越来越受关注.综述了以螺吡喃、螺噁嗪为光致变色基团的双功能光致变色化合体系的研究进展,主要介绍了具有荧光性能、与金属离子络合性能的光致变色体系的研究进展以及应用.     

含螺噁嗪类基团聚合物的合成及光致变色性能研究

合成了3种新型螺噁嗪类化合物(SP1~SP3),其分子结构中分别带有不同碳链长度的同类型取代基—(CH2)nBr;利用其活性基团C-Br与部分水解的聚甲基丙烯酸甲酯(h PMMA)反应制备了含SP1~SP3官能基的PMMA光致变色功能高分子材料(SP1~SP3-h PMMA).采用1H-NMR和IR对SP1~SP3结构进行了表征.研究了SP1~SP3及SP1~SP3-h PMMA的光致变色性能及其影响因素;研究了酸的加入和PMMA的水解率对SP1~SP3-h PMMA光致变色性能及热稳定性的影响.研究结果表明,与SP1、SP2比较,含最长碳链的SP3表现出优良的光敏感性和热稳定性;SP1~SP3-h PMMA的热稳定性均明显高于相应的SP1~SP3;盐酸的加入有利于提高SP-h PMMA的热稳定性;以水解率为9%的PMMA制备的SP3-9%h PMMA具有优异的光致变色性能和热稳定性.     

Deterioration of surface structure of lacquer films due to ultraviolet irradiation

The mechanism of deterioration due to ultraviolet irradiation of black (with iron ion) and kurome (translucent) lacquer films that had been dried at 15–20 °C in 60–70% relative humidity environment was revealed. The lacquer film changes were evaluated by observations of the surface by microscopy, IR, and XPS. A particulate material and toroidal shapes appeared in the black lacquer film during UV irradiation within 48 h, but they did not appear in the kurome lacquer film under UV irradiation before 240 h. The IR peak at ～3445 cm^?1 increased owing to the hydroxyl group, and the C 1s peak decreased and O 1s increased in the XPS spectra as the UV irradiation time increased, implying that a chemical reaction occurred on the surface of the lacquer film. On the top surface of the coating film, many toroidal shapes were observed in the black lacquer film, which showed that the black lacquer film deteriorated more quickly than the kurome lacquer film. In addition, the structural changes in the black lacquer film are also discussed in detail, on the basis of the results of the Py‐GC/MS measurement. Copyright © 2006 John Wiley & Sons, Ltd.     

有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的制备

将磺酸型聚酯多元醇、异佛尔酮二异氰酸酯（IPDI)和三羟甲基丙烷(TMP)在无有机溶剂参与的情况下进行预缩聚,以硅烷偶联剂γ-氨丙基三乙氧基硅烷（KH550）作为改性剂,加入双官能团单体甲基丙烯酸-β-羟乙酯(HEMA),得到含乙烯基和有机硅封端的聚氨酯作为种子乳液,然后与甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)混合单体共聚,合成了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液。 红外光谱的表征确定了有机硅改性磺酸型聚氨酯/丙烯酸酯复合乳液的化学结构;透射电子显微镜观察证实了此复合乳液具有明显的核壳结构;热重分析表明,经有机硅和丙烯酸酯改性后,胶膜的最大热失重温度提高了20 ℃,X射线衍射分析表明胶膜的结晶度降低,有利于提高膜的韧性。 力学性能测试及吸水率测试结果表明,当有机硅含量为1.9%时,胶膜的拉伸强度最高达到25.03 MPa,断裂伸长率为328%,此时膜的吸水率最低。     

双丙酮丙烯酰胺参与共聚的聚丙烯酸酯乳液的制备及其应用

肼;聚氨酯;乳液性质;交联;双丙酮丙烯酰胺参与共聚的聚丙烯酸酯乳液的制备及其应用     

Features of reaction amino-cyclocarbonate for production of new type nonisocyanate polyurethane coatings

We have studied different ways of preparing UV resistant oligomers with terminated cyclocarbonates, epoxy and amino groups. We have studied possibility of preparing HNIPU UV stable coatings. Linear and branched amino containing oligomers based on di- and tricyclocarbonates and primary diamines were investigated. It was found that oligomers should be used for curing epoxy-saturated resins, but since the residual quantity of amines this system can't be used for UV resistant coatings. The same problem was in system on the base of nonisocyanate epoxy-urethane oligomers cured by tertiary amines. Coating on the base of acrylic cyclocarbonates and oligomers with primary amines are similar to conventional polyurethane coatings on the base of acrylic hydroxyl containing oligomers and isocyanates, but mechanical properties and chemical resistance are better.     

Synthesis and photochromic properties of polymers containing spirooxazine groups

Two spirooxazine (SO) compounds containing bromobutyl substituents on 1-position (SO1) and 9′- position (SO2) have been synthesized and characterized by 1H-NMR, IR and ESI-MS in this paper. SO1-g-PMMA and SO2-g-PMMA polymer were prepared by grafting SO1 and SO2 onto PMMA through C-Br bonding sites. Also, SOs were doped into PMMA matrix to afford SO1-d-PMMA and SO2-d-PMMA. Photochromic behaviors of these compounds have been studied. Compared with SO1, SO2 exhibited better photoresponse and slower bleaching in dichloromethane solution. Inserted into polymer films, the decoloration process of SOs were significantly retarded and it was found that the fading curves fitted a first-order equation; As regard to four polymers, 1-position grafting (SO2-g-PMMA) can cause a higher reduction degree on the thermal fading rate.     

Incorporation of Reactive Corrosion Inhibitor in Waterborne Acrylic Polyurethane Coatings and Evaluation of its Corrosion Performance

Hydroxyl-epoxy phosphate (HEP) as a reactive corrosion inhibitor was innovatively synthesized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite (HEP-APU) coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.     

一种低分子量带有羧基的聚丙烯酸酯丙烯酸树脂的制备和性质

制备了一种紫外光固化预聚物——带有羧基的低分子量聚丙烯酸酯丙烯酸树脂(Polyacrylate acrylic resin, PAAR).其主链由丙烯酸烷基酯和丙烯酸进行共聚而得,当采用丙烯酸甲酯、丙烯酸乙酯和丙烯酸(摩尔比1:1:1)作为共聚单体,引发剂AIBN为1.5%,链转移剂十二硫醇为2.5%时,聚合得到的聚丙烯酸酯(Polyacrylate, PA)分子量在1100-1400之间,多分散性小于2,反应速率快,转化率高;由这种PA和甲基丙烯酸缩水甘油酯(GMA)进行酯化反应,制备得到最终产物聚丙烯酸酯丙烯酸树脂,酯化率可以达到80%以上,其光固化膜具有较好的涂膜硬度和柔韧性,光泽度饱满.     

Synthesis and Photochromism of Novel Spiro(indoline-2,3'-naphtho[2,1-b][1,4]oxazine)

A series of novel spirooxazine(SPO) derivatives containing nitrogen heterocycles was synthesized and characterized by ¹H NMR spectra, Fourier transform infrared(FTIR) spectra, mass spectra(MS) and elemental analysis, and their photochromic behaviors were fully investigated in solvents and polymer media. In solvents, they displayed excellent photochromism properties such as high photochromic response and fast thermal bleaching rate. Especially, compounds 1 and 4 exhibited strong fluorescence intensities in dichloromethane solution. It was additionally found that compound 4 showed high fatigue resistence in poly(methyl methacrylate)(PMMA) film, and the thermal decay curves were fitted with biexponential function in PMMA film.     

室温固化蓖麻油聚氨酯/乙烯基聚合物互穿网络材料的一些规律及其性能

研究了蓖麻油与甲苯二异氰酸酯及丙烯酸酯或苯乙烯等乙烯基单体在室温下生成的互穿网络聚合物(IPN)的一些规律及其性能.用红外光谱追踪表明,聚氨酯的生成快于甲基丙烯酸甲酯的聚合.研究IPN凝胶点指出.凝胶点时间随聚氨酯含量增加及聚苯乙烯含量减少而缩短.丙烯酸甲酯在生成IPN过程中凝胶的生成速度要比苯乙烯的场合快.丙烯酸丁酯、丙烯腈或丙烯酸甲酯与蓖麻油聚氨酯生成的IPN的抗张强度在聚氨酯占一半时呈现最大值.透射电镜观察表明,生成速率较快的聚氨酯的微区存在于聚丙烯酸甲酯中.聚丙烯酸甲酯与蓖麻油聚氨酯形成的IPN在tanδ-T,曲线上呈现一个宽的玻璃化转变温度.     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用共聚的方法制备出丙烯酸酯改性的水性聚氨酯共聚乳液(PUA乳液),并对PUA乳液的制备方法和工艺、耐溶剂性、机械稳定性进行了初步的研究。结果表明,具有IPN结构的PUA乳液耐溶剂性、机械稳定性比水性PU有明显的提高。