Chain transfer polymerisation of poly-N-alkylacrylamides in superheated methanol and by microwave induction

The chain transfer polymerisation (telomerisation) of poly-N-isopropylacrylamide (PNIPAM), poly-N,N-dimethylacrylamide (PNDMAM) and poly-N-{3-(dimethylamino)propyl}acrylamide (PN3DMAPAM) as well as of co-polymers of PNIPAM and PNDMAM were studied. Reactions in superheated yet subcritical methanol (80-170 °C) and—under solvent free conditions—induced by microwave irradiation were compared in terms of product yield and quality to those obtained under standard reflux conditions (methanol reflux, ∼65 °C, ambient pressure). In superheated methanol the reaction time was reduced by 66%, the average molar mass and the yield (monomer conversion) remain largely unchanged. Dielectric heating reduces the reaction time even further, i.e. to the minute range. Surprisingly, the average molar mass of the polymers dropped by 30% in these experiments, an effect that is most likely caused by the higher polarity of the reaction mixture under solvent-free conditions.     

Double UV polymerisation with variable temperature-controllable selective reflection of polymer-stabilised liquid crystal (PSLC) composites

In this study, a method of preparing wide-band reflection cholesteric liquid crystals (CLCs) films by UV-radical polymerisation in combination with UV-cationic polymerisation is proposed. Because the helical twisting power (HTP) of the chiral dopant decreases with increasing temperature and the polymerisation rate of UV-initiated free radical polymerisation is faster than UV-initiated cationic polymerisation, by adjusting the temperature, broadband reflective films with non-uniform pitch distribution are obtained. The fractured surface of the polymer network of the broadband reflective films is observed by scanning electron microscopy (SEM), which reveals the presence of non-uniform pitch distribution. In addition, the influences of monomer concentration, UV light intensity and UV curing time on the consequent non-uniform pitch distribution have been studied.     

Novel oxazepinedione-derived symmetric dimers: synthesis and mesophase characterisation of seven-membered heterocyclic compounds

The synthesis and characterisation of three sets of symmetric dimeric compounds composed of seven-membered oxazepinedione heterocyclic rings were carried out. All the dimers possess the tetradecyl- (n = 14) alkyl side chain attached to the nitrogen atom of the oxazepinedione core. The oxazepinedione core in turn was connected with varied connecting spacers (n = 4, 6, 8, 10 and 12). The dimers were spectroscopically characterised by FT-IR, ¹H-NMR, ¹³C-NMR and elemental analysis techniques. The compounds were investigated for liquid crystalline properties using differential scanning calorimetry and polarising optical microscopy with heating assembly. The precursor imines 2a–e itself started exhibiting liquid crystalline SmA/tilted hexatic mesophase. Further fusion of 2a–e with maleic anhydride, succinic anhydride and phthalic anhydride gave the novel oxazepinedione-derived symmetric dimers 3a–e, 4a–e and 5a–e respectively. The dimers 3a–e and 4a–e did not exhibit any liquid crystal (LC) properties. However, the phthalic anhydride-fused oxazepinediones 5a–e show monotropic nematic liquid crystalline phase. The results indicate that the formation of mesophase is dependent on the type of fused oxazepinedione ring.     

二代树状碳硅烷液晶研究——端基含36个己氧基偶氮苯介晶基元

用发散法合成周边含36个己氧基偶氮苯介晶基元(M3)端基的新的二代树状碳硅烷液晶(D2),并用元素分析、氢谱、激光质谱、红外光谱、紫外-可见光谱、偏光显微镜,DSC和WAXD法进行表征.D2为向列相,与M3相同.D2液晶态相行为是K90N105I1l3N75K,D2熔点比M3降低2633℃,D2清亮点比M3降低315℃,D2液晶态温区比M3加宽1130℃.D2和一代树状物D1的相态由介晶基元相态决定.D2熔点比D1降低23℃.D2清亮点比D1降低1121℃,D2液晶态温区比D1减少819℃.     

含Sc*相硅碳烷树枝状分子液晶

树枝状化合物具有规整的结构,其分子体积、形状和功能基可在分子水平上精确控制[1].它的出现对于经典的有机高分子界是一个冲击,它是化学、生命科学和材料科学等多学科的交叉点,成为当前学术界的一大研究热点.我国这方面的研究起步较晚,至今仅有陈永明[2]、薄志山[3]和我们[4]曾报道过树状物.     

Studies on Liquid Crystalline Bis[4-(p-phenoxy)-phenylbenzoate]-Alkyldicarboxylate

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New divalent samarocenes for butadiene polymerisation: influence of the steric effect and the electron density on the catalytic activity

Two new divalent samarocenes, Cp^*′₂Sm(THF) (1) and (Cp^Ph3)₂Sm(THF) (2) (Cp^*′=C₅Me₄ⁿPr, Cp^Ph3=H₂C₅Ph₃-1,2,4), were synthesized and characterized by ¹H NMR and elemental analysis. The activity of 1 and 2 as butadiene polymerisation catalysts was studied, in the presence of MAO and MMAO, and compared to this of Cp^*₂Sm(THF)₂ (3) and (Cp⁴ⁱ)₂Sm (4) (Cp^*=C₅Me₅, Cp⁴ⁱ=C₅HⁱPr₄), in the same conditions. The 1/MAO system presents the highest activity. The less active 2/MAO system leads to a high cis-1,4 regular structure up to 97%. The MMAO cocatalyst is found very sensitive to the steric hindrance of the samarocenes: the activity decreases from 1/MAO to 1/MMAO, and no activity is observed in the case of complexes 2 and 4, associated to MMAO. Complexes 1 and 2 can be both oxidized with AlMe₃ to give the corresponding Sm/Al bimetallics and , respectively.     

Synthesis and mesomorphism of the liquid crystal based on diosgenyl end-capped polycarbonate

ABSTRACT

To enhance the activity of the hydroxyl group of diosgenin, the diosgenyl derivative Dios–(CH₂)₆–OH with an alkyl spacer and end primary hydroxyl group was synthesised via the chain extension reaction between diosgenin and 1,6-hexanediol. Then the liquid crystal (LC) compounds Dios–(CH₂)₆–(trimethylene carbonate [TMC])_n with different TMC content were obtained via the ring-opening polymerisation of TMC with Dios–(CH₂)₆–OH as initiator and mesogenic unit, importantly, there was no catalyst added. The chemical structures of the Dios–(CH₂)₆–OH and Dios–(CH₂)₆–(TMC)_n were characterised by Fourier transform infrared (FT-IR) spectra and ¹H NMR. The mesomorphism was characterised by polarising optical microscopy and X-ray diffraction measurement, and the phase transition was investigated by differential scanning calorimetry. The results showed that Dios–(CH₂)₆–(TMC)_n displayed an enantiotropic smectic phase, and TMC content played an important role in the LC properties of Dios–(CH₂)₆–(TMC)_n. The higher the TMC content, the lower the phase transition temperature of Dios–(CH₂)₆–(TMC)_n.     

超声陈化法制备纳米NaY分子筛及形成机理研究

Nano-sized NaY zeolite was synthesized from metakaolin in the hydrothermal synthesis system by using ultrasonic during aging time.The process of crystallizing NaY zeolite was studied by XRD、SEM、ICP OES ,and the formation mechanism of nano-sized NaY zeolite was researched,finally the conditions of synthesizing nano-sized zeolite NaY had been brought forward.     

The influence of flexible spacer and the chirality of the core on the formation of chiral nematic phase of symmetric dimers containing trifluoromethyl terminal

Seven symmetric liquid crystal (LC) dimers containing different chiral cores and LC arms have been synthesised, termed EPDA-(R,S)PD, TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD, TFBA-(R)PD, TFBDA-IB and TFBA-IB, respectively. TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD and TFBDA-IB displayed chiral smectic A (SmA*) phase, while EPDA-(R,S)PD, TFBA-(R)PD and TFBA-IB exhibited chiral nematic (N*) phase. The effects of flexible spacer, structural type of LC arms and the chirality of the cores on the thermal properties of the dimers and the formation of N* phase have been studied. The results indicated that the chiral core was prone to induce the N* phase in LC dimer that contained nematic arms although the chirality of the core is very weak, while for the smectic LC arms containing CF3 terminal, the removal of the flexible spacer between chiral core and rigid LC units was conducive to the formation of N* phase. For example, TFBDA-(R)PD and TFBDA-IB displayed SmA* phase, while TFBA-(R)PD and TFBA-IB exhibited N* phase. However TFBA-(R,S)PD did not display N* phase, which reminded us that the chirality of the core and the conformation of the dimer also played an influence in the formation of the LC phase.     

N,N-二甲基正十二烷基胺/无机含氧酸体系的相态结构研究

利用拟三元相图法研究了N,N-二甲基正十二烷基胺(DMDA)多元体系的相态结构,并用电导、偏光显微镜以及红外、紫外可见光谱等手段进行了表征.发现N,N-二甲基正十二烷基胺体系随水相含量的增加,铵盐发生不同形式的有序缔合,分别形成了W/O型微乳液、“节-结”型链状缔合体、层状液晶和O/W型微乳液;在层状液晶中,SO₄^2-主要以桥式双齿配位形式存在,中性胺分子有利于体系中液晶的形成;层状液晶于500nm波长处有一吸收峰,在430nm附近发生“光短路”现象,该现象可能对测定层状液晶的层间距有重要意义.     

六棱柱状多晶γ-Al2O3的制备、表征及其形成机制研究

以AlCl₃·6H₂O为前驱物,在氨水介质中用水热法制备了具有新颖形貌特征的六棱柱状多晶γ-Al₂O₃颗粒。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)及N₂物理吸脱附等方法对所制备的γ-Al₂O₃颗粒进行了表征,并对其形貌形成机制进行了分析。结果表明,铝前驱物在氨水介质中通过水热处理后,经焙烧可以形成形貌规整的六棱柱状γ-Al₂O₃颗粒,其边长与长度分别约为0.3 μm和2.5 μm。TEM图片显示,六棱柱颗粒是由尺寸在10 nm左右的粒子聚集而成,因而具有多晶γ相特征。所制备的γ-Al₂O₃材料具有发达的孔隙结构,比表面积为274 cm²/g,孔容为0.51 cm³/g,孔径集中分布在5.5 nm周围。研究发现,γ-Al₂O₃六棱柱形貌的形成机制与AlOOH二次粒子在NH₄⁺正电荷作用下发生的最稳态排列形式具有密切的关联。     

Progress in the study on the composition and formation mechanism of gallstone

Our serial studies from 1970s on chemical composition, structure determination and formation mechanism of gallstones were reviewed. The chemical component investigation of brown-pigment gallstone demonstrated that it consists of macromolecules such as proteins, glyco-proteins, polysaccharides, bilirubin polymers and pigment polymers, and biomolecules such as cholesterol, bile salts, calcium salts of carbonate, phosphate, fatty acids and bilirubinate as well as various metal ions. The binding of metal ions with bile salts and bilirubin plays important roles in gallstone formation, i.e., calcium bilirubinate complex is the major constitute of brown-pigment gallstones, and copper bilirubinate complex is critical in the black color appearance of black-pigment gallstone. The cross section of many gallstones exhibits a concentric ring structure composed of various small particles with a fractal character. This is nonlinear phenomenon in gallstone formation. A typical model system of metal ions-deoxycholate (or cho     

Synthesis and properties of new ionic liquid crystals based on para-nitroazobenzene with substitution vinylimidazolium ion group

A new series of ionic liquid crystals (ILCs), 1-(4-(4-nitrophenylazo)phenyloxy) vinyl-3-methyl-1H-imidazol-3-ium bromide salts (C _n , n?=?6, 10) were synthesised. Their chemical structures were determined by ¹H NMR, ¹³C NMR, UV spectroscopy and elemental analysis. The liquid crystalline properties were investigated by differential scanning calorimetry, polarising optical microscopy, and powder X-ray diffraction. These measurements showed that C _n (n?=?6, 10) exhibit smectic liquid crystalline phases with focal-conic fan-shaped textures. The introduction of vinylimidazolium group onto the azobenzene enhances the thermal stability of the smectic state, which play an important role in forming the smectic layer structure.     

Liquid Crystalline Properties of Side-chain Polymers Bearing the Same Mesogenic Group

The synthesis and properties of a series of new ferroelectric liquid crystal side-chain polymers with the same mesogenic side group but different polymer backbones (polyacrylate, polymethacrylate and polysiloxanes) are described. The polymorphism is studied by optical microscopy, differential scanning calorimetry and X-ray diffraction. All the monomers exhibit at least an S_A and a ferroelectric S*_C phase, as the polymethacrylate and the copolysiloxane. These two polymers and the polyacrylate exhibit also an S*_F phase. © 1997 John Wiley & Sons, Ltd.     

The mechanism of formation of copper aluminide in the thermal explosion mode

The mechanism of formation of copper aluminides in the thermal explosion mode was studied. A molded mixture of copper and aluminum powders was heated to the self-ignition temperature by the radiation of a tungsten heater. The phase transformations were detected by time-resolved X-ray diffraction (TRXRD). The kinetics of heat release due to the chemical reaction was studied by measuring the temperature of the sample. The macrokinetic stages of the process were revealed, and the apparent activation energy of each stage was estimated.     

富勒烯形成机理的研究进展

富勒烯的形成机理多年来一直是富勒烯科学研究的焦点问题,科学家们用大量的理论计算和实验工作来探索富勒烯的形成过程,并提出了多种模型和可能机理．根据富勒烯形成途径的不同,这些机理可分为“自下而上”、“自上而下”或“先上后下”3种生长方式,但是由于缺乏足够的实验证据,至今还没有一种机理得到实验事实的完全证明并被普遍接受．本文就近年来有关富勒烯形成机理的研究进行了归纳阐述,并概述了其中影响较大的几种机理．     

Characterisation of different inulin samples by DSC: Influence of polymerisation degree on melting temperature

Melting behaviour of powder inulin has been studied by differential scanning calorimetry. DSC curves show two endothermic peaks, relative to water elimination and to inulin melting, respectively. The second peak is dependent on inulin type and a shift to a higher temperature is observed with increasing average polymerisation degree (DP) of the sample. For similar crystallinity index, linear relations have been underlined and so predicting inulin mean DP can be done by DSC analysis. The study shows that a relatively high heating rate (25°C min^–1) can be used and brings a supplementary interest by an important reduction of analysis time.This revised version was published online in November 2005 with corrections to the Cover Date.     

过渡金属表面上水生成经典Horiuti-Polanyi机理与非Horiuti-Polanyi机理选择的总体趋势（英文）

在非均相催化加氢反应中,氢气(H₂)一直被公认为是通过两步基元步骤参加还原反应的,包括第一步的分子解离和之后的反应物与原子氢键合,即所谓的Horiuti-Polanyi(HP)机理.直到我们研究组在Ag或Au催化丙烯醛加氢还原反应理论研究中发现非HP机理加氢路径存在时,新的机理才被提出,并引起广大研究者的浓厚兴趣.考虑到表面羟基(OH)和氧(O)在非均相催化体系中广泛存在,如常见的过渡金属催化的费托合成、甲烷重整、水汽转化及氨氧化等反应,基于第一性原理的密度泛函理论计算方法,我们对OH/O在一系列过渡金属催化作用下还原生成水的微观机理进行了系统全面的探究.研究发现,不同金属对应于不同的催化氢化反应活性,以及不同的催化反应机理.在某些金属上H₂以分子形式进攻反应物种的非HP机理有利,而在其它金属上经典的H₂解离后参与氢化还原反应的HP机理更容易发生.详细分析显示, H₂的解离活性决定了反应机理的种类:在对H₂解离具有催化活性的金属(如Pt、Ni)表面,不论是(211)台阶面还是(...     

不同形貌纳米二氧化硅的制备及形成机理研究

在水醇体系中,以正硅酸四乙酯(TEOS)作为硅源、氨水作为催化剂,快速合成了哑铃状、纤维状及链状3种形貌的纳米SiO2;利用透射电子显微镜分析了产物的微观结构,着重探讨了氨水浓度、TEOS浓度及TEOS滴加速度对纳米SiO2形貌的影响,并提出了不同形貌纳米SiO2的形成机理.