以硫醚为主链的螯合树脂研究：Ⅲ含硫氰酸根树脂的合成及吸附…

环硫氯丙烷的均聚物或环硫氯丙烷与环氧氯、丙烷的共聚物，在少量二乙烯三胺存在下制得预交联聚合物，将后者与硫氰化钾反应，制得两种侧链带有硫氰酸根的新型螯合树脂。它们对贵金属具有优良的吸附性能和高的吸附选择性。通过Ｘ射线光电子能谱初步探讨了树脂对金属离子的螯合作用。     

非对称环硫乙烷的区域选择性亲核开环反应

环硫乙烷与它的氧类似物环氧乙烷和氮类似物氮杂环丙烷一样,是一类重要的有机合成中间体,在医药和农用化学品工业领域也得到广泛应用。通过开环和异构化反应,还广泛用于制备硫醇和硫醚等含硫化合物。本文总结了常用亲核试剂对非对称环硫乙烷的亲核开环反应及其区域选择性。环硫乙烷的亲核开环反应通常只受空间效应影响,亲核试剂进攻非对称环硫乙烷位阻小的碳原子,对于烯基取代的环硫乙烷有时可以进攻烯基的β碳原子发生SN2’开环反应。强亲核性的亲核试剂容易致使环硫乙烷脱硫生成烯烃,而亲核性相对较弱的亲核试剂容易发生多聚反应生成多硫醚。在Lewis酸存在下,电子效应会对开环反应的区域选择性产生影响,甚至起主导作用。虽然烷基取代环硫乙烷在Lewis酸存在下的开环仍然主要发生在其取代基少的碳原子上(位阻控制),但受电子效应影响,芳基和烯基取代环硫乙烷的亲核开环,其亲核试剂一般倾向于进攻环硫乙烷的芳甲位和烯丙位碳原子(电子效应控制)。     

以硫醚为主链的螯合树脂研究Ⅳ．含硫代硫酸根、叠氮基树脂的合成及吸附性能

聚环硫氯丙烷或环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联预聚物，将交联预聚物分别与硫代硫酸钠，叠氮化钠反应，制得四种侧链带有硫代硫酸根或叠氮基的新型螯合树脂。它们对贵金属离子具有较高的吸附容量和较好的吸附选择性。     

2-氰基-2,3-二甲基-3-甲基羰甲基-5-硫酮-吡咯烷的合成

2-氰基-2;3-二甲基-3-甲基羰甲基-5-硫酮-吡咯烷的合成;双甲基环并内酯;双甲基环并内酰胺-内酯;氰基吡咯烷酮;氰基吡咯烷硫酮     

含四硫富瓦烯大环化合物的合成与研究进展

简要介绍了含有四硫富瓦烯(TTF)单元的大环化合物的分类, 概括了各类含四硫富瓦烯大环化合物的合成方法, 主要包括含有1,3-二硫杂环戊烯-2-硫酮单元的大环化合物在亚磷酸三烷基酯参与下的偶合反应, 以及带有氰乙基硫等取代基的预先合成的官能化TTF与二卤代低聚醚的反应. 综述了含四硫富瓦烯大环化合物的电化学性能及其在分子识别方面应用研究的最新进展, 提出了含四硫富瓦烯大环化合物的发展趋势.     

四硫富瓦烯和蒽单元构建的新型多功能四硫富瓦烯环蕃的合成与性质

2,6-二(甲硫基)-3,7-二(2-氰乙基硫基)四硫富瓦烯在甲醇钠的作用下消除保护基团, 生成四硫富瓦烯双钠盐, 再与9,10-二(氯甲基)蒽反应生成由四硫富瓦烯(TTF)和蒽单元构建的新型TTF环蕃. 分别通过循环伏安法和化学氧化法对其电化学性质、紫外吸收光谱和荧光性质进行了研究, 实验结果表明此类TTF环蕃化合物对OH^－离子有识别功能. 并通过电化学和紫外吸收光谱研究了这种新型四硫富瓦烯环蕃在金纳米颗粒表面自组装行为.     

以硫醚为主链的螯合树脂研究——Ⅲ.含硫氰酸根树脂的合成及吸附性能

环硫氯丙烷的均聚物或环硫氯丙烷与环氧氯丙烷的共聚物,在少量二乙烯三胺存在下制得预交联聚合物,将后者与硫氰化钾反应,制得两种侧链带有硫氰酸根的新型螯合树脂。它们对贵金属具有优良的吸附性能和高的吸附选择性。通过X射线光电予能谱初步探讨了树脂对金属离子的螯合作用     

α,β—不饱和硫酮体系[4＋2]环加成反应的研究

系统研究了β,β-不饱和硫酮在[4+2]环加成反应中的行为.选取5-芳亚甲基四氢噻唑-2,4-二硫酮作为反应的杂共轭双烯体系,与N-苯基马来酰亚胺等嗜双烯作用,得到12个新化合物.观察到丙烯酸乙酯和丙烯腈在对杂共轭双烯进行[4+2]环加成反应时存在着某种区域选择性.初步探讨了这类环加成反应条件及反应物的反应活性.     

螯合树脂研究 Ⅻ.以聚硫醚为主链的异丙巯基胺树脂的合成及其吸附性能

由聚环硫氟丙烷与多乙烯多胺反应制得的聚合物(PB)再与环硫丙烷反应,合成了四种以聚硫醚为主链的异丙巯基胺树脂(PBM_1-4)。树脂对Au~(3+)、Pd~(2+)、Pt~(4+)、Ag~+和Hg~(2+)等离子具有强的吸附能力,对Cu~(2+)次之,对Zn~(2+)和Pb~(2+)很弱。树脂对贵金属具有高的选择性,能从含Au~(3+)、Cr~(3+)、Co~(2+)、Ni~(2+)、Cu~(2+)、Mn~(2+)、Zn~(2+)和Fe~(3+)的溶液中定量吸附Au~(3+)而不吸附其它离子。     

α—氧代烯酮环二硫代缩酮化学：α,α—二氧代烯酮环二硫代缩酮与乙二…

由α，α－二氧代烯酮环二硫代缩酮与乙二胺反应制得五种α，α－二氧代烯酮环二氮代缩酮化合物，所有产物均经元素分析，ＩＲ＾１ＨＮＭＲ和＾１３ＣＮＭＲ确证。     

含硫高折射率光学树脂合成及性能研究进展

作为无机玻璃的替代品,有机光学树脂具有轻质、抗冲击性好、易加工和可调性强等优点。折射率是光学树脂的主要参数之一,折射率的高低可直接影响成品镜片的厚度、美观性和舒适度。在不降低光学树脂综合性能的基础上提升光学树脂折射率一直是该领域的热点和难点,在光学树脂中引入高摩尔折射率的硫元素被认为是最有效和常用的方法之一。本文将含硫光学树脂分为烯烃类、环氧类、环硫类、多环类和聚氨酯类,简要综述了国内外近几年的研究进展,涉及单体合成、单体聚合以及单体结构对光学树脂综合性能影响,系统总结了以上材料的特性及发展。     

HIGH INDEX OPTICAL MATERIALS PREPARED BY COPOLYMERIZATION OF NOVEL BIFUNCTIONAL THIOMETHACRYLATES

Optical materials, such as ophthalmic lens, are thermosetting resins, which require crosslinking agents. An optical resin, having a high refractive index, is usually produced by radical copolymerization in which high index crosslinking monomers are significantly important. We provide here the resins prepared by radical polymerization of novel bifunctional thiomethacrylates as high index crosslinkers.     

新型复合环氧光学树脂的制备与性能研究

通过2,2-二巯基乙硫醚(MES)与环氧氯丙烷反应合成了2,2-二巯基二乙硫醚二缩水甘油醚型环氧树脂(DGEMES),通过FTIR和MS对其进行表征;用乙二胺作为固化剂,将DGEMES与双酚A型环氧树脂(DGEBA)复合固化,得到了新型高折射率和低色散的光学树脂.DGEMES是一种较好的共聚单体,可以同时提高共聚树脂的折射率和阿贝数;DGEBA/DGEMES/乙二胺共固化树脂的nd=1.59～1.62,νd=35～39;当DGEMES的质量分数为40%时,固化树脂的折射率达到1.60以上,冲击强度22.5kJ/m₂,且其它性能较均衡.此外,以甲基六氢苯酐(B-650)为固化剂,还合成了具有中等折射率的DGEBA/DGEMES/B-650共固化树脂(nd=1.54～1.56,νd=38～40),并对其光学和机械性能进行了研究.     

高折射率有机/无机纳米杂化透明膜层材料的制备与性质研究

采用溶胶-凝胶法,将钛酸酯和硅烷偶联剂(KH-560)进行共水解,经涂膜、固化,制备了一系列含有无机二氧化钛纳米相的无机/有机杂化膜层材料,通过不同方法对杂化膜层的微结构、光学、机械和热性质进行了表征.结果表明,所得到的有机/无机纳米复合膜层,在可见光范围内的透过率均在90%以上,同时具有较好的耐热性和较高的折射率(nd=1.47~1.73),并且膜层与基材的附着性好,铅笔硬度达到4~5H.     

High refractive index adamantane‐based silicone resins for the encapsulation of light‐emitting diodes

The encapsulation of high power light emitting diode (LED) needs the silicone resins to have relative high refractive index and thermal‐aging properties. Herein, high refractive index adamantane‐based phenyl epoxy‐silicone (APES) resins for LED encapsulation were synthesized by the sol‐gel condensation of 1‐adamantane methanol propyltrimethoxysilane‐3‐urethane, γ‐(2,3‐epoxypropoxy)propytrimethoxysilane and diphenylsilanediol. These adamantane‐based silicone resins have multifunctional groups including adamantyl group, phenyl group, and epoxy group in order to meet the various requirements for LED encapsulation. Importantly, the adamantane group in the silicone resins benefits for high refractive index and anti‐thermal properties. These APES resins were characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. When APES resins were cured by methylhexahydrophthalic anhydride, they showed relatively high refractive index of 1.56, high hardness, and high thermal resistance. The encapsulated LED demonstrated high adhesion properties by red‐ink tests. These merits make adamantane‐based silicone resins promising candidates as LED encapsulation materials.     

High-refractive index acrylate polymers for applications in nanoimprint lithography

The development of polymeric optical materials with a higher refractive index,transparency in the visible spectrum region and easier processability is increasingly desirable for advanced optical applications such as microlenses,image sensors,and organic light-emitting diodes.Most acrylates have a low refractive index(around 1.50)which does not meet the high perfo rmance requirements of advanced optical materials.In this research,three novel acrylates were synthesized via a facile one-step approach and used to fabricate optical transparent polymers.All of the polymers reveal good optical properties including high transparency(≥90%)in the visible spectrum region and high refractive index values(1.6363)at 550 nm.Moreover,nanostructures of these acrylate polymers with various feature sizes including nanogratings and photonic crystals were successfully fabricated using nanoimprint lithography.These results indicate that these acrylates can be used in a wide range of optical and optoelectronic devices where nanopatterned films with high refractive index and transparency are required.     

Quantitation and test of enantiomeric purity of the L-ketohexoses by liquid chromatography with dual refractive index and laser-based chiroptical detection

Experimental data for the synthetic methods of preparation of the L-ketohexoses have been lacking an analytical method for monitoring the chemical or enzymatic reactions described. Dual refractive index and laser-based chiroptical detection provides an ideal method for following the reactions, since the refractive index detector quantifies the amount of analyte, while the ratio of optical rotation to refractive index response allows the enantiomer mole fraction to be determined. Sulfonated polystyrenedivinylbenzene resin in the Ca form as the stationary phase with H2O at 80 degrees C as the eluent gives base-line separation of sorbose, fructose, tagatose, and psicose. Dependent on the complexity of the reaction mixture, analysis times range from 20 to 60 min.     

Synthesis and Characterization of Highly Oriented Sol-Gel (Pb, La) TiO3 Thin Film Optical Waveguides

The preparation and the optical characteristics of highly oriented PLT thin films are investigated. PLT films fabricated on MgO(100) and c-plane sapphire substrates have highly grown in (100) and (111) orientations, respectively. PLT films with high La content have a near cubic structure and weak anisotropy of refractive indices. The optical propagation losses of PLT films decrease as the La content of the films increases due to a complex interaction of surface roughness reduction and a reduction in the anisotropy refractive index. However, optical scattering in thicker sol-gel PLT thin film waveguides occurs by the internal scattering mechanism from the defects and the interfaces rather than by the surface scattering mechanism.     

新型聚(甲基)丙烯酸酯/盐透明材料的制备及其性能

聚(甲基)丙烯酸酯具有优异的透光性、耐光性和耐候性,广泛用作光学塑料.研制高折射率、高耐热性、低吸湿性的透明高分子材料是近年来光学塑料研究和开发的重点之一.本文介绍了新型聚(甲基)丙烯酸酯/盐透明高分子材料的主要制备方法,即新型单体合成-聚合法、共聚法、共混-聚合法和有机-无机纳米杂化法,并系统地总结了各方法的特点以及所制备的材料的性能,展示了目前应用最为广泛的新型单体合成-聚合法和有机-无机纳米杂化法的潜在的应用前景.     

新型含硫高折光指数光学树脂单体MPSDMA的合成及其共聚树脂的性能研究

通过氯磺化反应,还原反应和低温相转移仙化反应合成了一种新型光学树脂单体合成 4,4′-二巯基二苯硫醚双甲基丙烯酸酯（MPSDMA）,。成功地将苯环、含硫基团和双键引入光学树脂单体结构中,将MPSDMA分别与甲基丙烯酸甲酯（MMA）和苯乙烯（St)通过自由基共聚制成透明树脂,共聚树脂性能的研究表明该类新型光学树脂具有高折光指数,高表面硬度等特点。