A DSC-Study of Donor/Acceptor Side-Chain Polymers with Flourinated Taper-Shaped Tails

It is shown that insertion in methacrylic polymers of bulky electron donor/acceptor side-groups with taper-shaped flourinated tails promotes a self-organization of the respective side-chain polymers due to the space demands of the bulky D/A side-groups, leading to a columnar hexagonal mesophase. The presence of an Lc-phase is evidenced by DSC and identified by X-ray analysis. The orientation in the respective copolymers and polymer blends is additionally improved by the CT-interaction between the D/A side-groups. An increased packing effect due to this CT-orientation effect is evidenced in DSC by an increase of the respective transition temperatures. CT-interaction is responsible as well for a preferential polymerization of monomeric D/A-complexes leading to copolymers of alternating structures and for a zip-like arrangement along the main chain of the A/D-complexes between the interacting side-groups in polymer blends. Formation of mesophases is even observed in CT-interacting blends between the Lc-D/A side-chain polymethacrylates and the respective amorphous D/A side-chain polysiloxanes.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effects of structural imperfections on the dynamic mechanical response of main-chain smectic elastomers

We examine the influence of structural imperfections on mechanical damping in polydomain smectic main-chain liquid crystalline elastomers (MCLCE) subjected to small strain oscillatory shear. The mechanical loss factor tan δ = G″(ω)/G′(ω) exhibits a strong maximum (tan δ ≈ 1.0) near the smectic-isotropic (clearing) transition. “Optimal” elastomers that exhibit minimal equilibrium swelling in a good solvent are compared with highly swelling “imperfect elastomers” that contain higher concentrations of structural imperfections such as pendant chains. For the imperfect elastomers, tan δ is markedly enhanced in the isotropic state because of relaxation of pendant chains and other imperfections. However, within the smectic state, the magnitude of tan δ and its temperature dependence are similar for optimal and imperfect elastomers at ω = 1 Hz. The prominent loss peak near the clearing transition arises from segment-level relaxations that are insensitive to the details of chain connectivity. Smectic MCLCE can be tailored for applications as vibration-damping materials by manipulating the clearing transition temperature through the backbone structure or by deliberate introduction of structural imperfections such as pendant chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3267–3276, 2007     

Finkelstein Reaction in Functionalized Crown-ether Ionic Liquids

Recent years, crown ethers have been used in many fields, including phase transfer catalysis, chromatography stationary phase, ionselective electrode, and concentration of metal ions, etc1.. However, the toxicity of free crown ethers makes them unsuitable for industrial use2. Introduction of a crown ether as a functional group to functionalized ionic liquids has been reported3. These functionalized ionic liquids will combine the excellent properties of crown ether and ionic liquids without los…     

New fluorinated polysiloxanes containing an ester function in the spacer. I. Synthesis and characterization

Unsaturated perfluoroalkyl esters derived from undecylenic acid: CH₂?CH? (CH₂)₈? COO? CH₂? CH₂? R_F (with R_F?C₆F₁₃, 2a and R_F?C₈F₁₇, 2b ) and C₈F₁₇? (CH₂)₁₀? COO? CH₂? CH?CH₂, 2c were prepared with excellent yields. Their hydrosilylation by methylhydrodimethylsiloxane copolymers of various Si? H contents gives new fluorinated polysiloxanes which were examined by ¹H- and ¹³C-NMR, GPC, differential scanning calorimetry, and optical polarizing microscopy. Polymers derived from compounds 2a and 2b exhibit mesomorphic structures. © 1994 John Wiley & Sons, Inc.     

(R)-2,3-Cyclohexylideneglyceraldehyde, a novel template for facile and simple entry into chiral hydroxy γ-lactones: synthesis of (−)-muricatacin

(R)-2,3-Cyclohexylideneglyceraldehyde 1 has been used in a simple and efficient synthesis of (−)-muricatacin 10. The required chiron, syn-alkanetriol 2a was prepared by the reduction of a ketone 3 derived from 1.     

Solid State NMR and TG/MS Study on the Transformation of Methyl Groups During Pyrolysis of Preceramic Precursors to SiOC Glasses

The sol-gel method was used to prepare two different starting gels containing SiCH₃-groups for the preparation of SiOC ceramics. To understand the role of Si—H bonds in the incorporation of carbon into the SiOC network, gels prepared from a 1:2 mixture of triethoxysilane and methyldiethoxysilane (T^HD^H2) and solely methyltriethoxysilane (T^Me) were investigated. Thermogravimetric analysis coupled with mass spectroscopy (TG-MS) in inert atmosphere was performed to attain an insight into the decomposition reactions involved during gel-glass transformation. Samples calcined at different temperatures up to 1000°C were characterized by ²⁹Si and ¹³C magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. The presence of SiH groups in the starting gel allows an efficient conversion of Si—CH₃ groups into CSi₄ sites at lower temperatures. As a result, despite a much lower amount of carbon in the starting T^HD^H2 gel (C/Si = 0.33) compared to the T^Me gel (C/Si = 1), the amount of carbon inserted into the SiOC network of both glasses is equivalent, but the T^Me sample contains the 10 fold amount of free carbon.     

新型螯合树脂在线预富集测定海水中痕量Cd

将新型螯合树脂(XAD-H2Dz)应用于微柱现场在线采样(MFS)新技术中,实现了海水样中痕量Cd的在线原位预富集和实验室中流动注射-火焰原子吸收(FI-FAAS)系统的联机测定。采样体积为5 mL和50 mL时,检出限(3σ)分别为68和6.7 ng/L;相对标准偏差(n=7)分别为2.0%和2.6%。对国家海水微量元素标准物质GBW(E)080040和实际样品(大连老虎滩区域海水以及连云港黄海水域)中镉进行分析,均获得了满意的结果。     

Highly stretchable and self-healing hydrogels based on poly(acrylic acid) and functional POSS

Herein, we present a novel way for the production of self-healing hydrogels with stretch beyond 4200% than their initial length and relatively high tensile strength(0.1?0.25 MPa). Furthermore, the hydrogel was insensitive to notch. Even for the samples containing V-notches, a stretch of 2300% was demonstrated. The hydrogels were developed by in situ crosslinking of the self-assembled colloidal poly(acrylic acid)(PAA)/functionalized polyhedral oligomeric silsesquioxane(POSS) micelles. This was achieved by the addition of functionalized polyhedral oligomeric silsesquioxane with tertiary amines and hydroxyls(POSS-AH) into the PAA reaction solution. The POSS-AH led to micellar growth, then the dualcrosslinked network was constructed. One type of crosslink was formed by hydrogen-bonding and ionic interactions between PAA chains and POSS-AH, the other type of crosslink was formed by covalent bonds between PAA and bis(N,N'-methylenebis-acrylamide).     

Viscoelastic response and interlaminar delamination resistance of epoxy/glass fiber/functionalized graphene oxide multi-scale composites

Graphene oxide (GO) was functionalized using three different diamines, namely ethylenediamine (EDA), 4,4′-diaminodiphenyl sulfone (DDS) and p-phenylenediamine (PPD) to reinforce an epoxy/glass fiber (EP/GF) composite laminate, with the aim of improving the overall composite mechanical performance. Different mechanical characterization techniques were used to determine the mechanical performance, including: tensile stress strain, double cantilever beam (DCB) mode-I fracture toughness and dynamic mechanical thermal analysis (DMTA). Scanning electron microscopy (SEM) was used to support the results and conclusions. The results demonstrated remarkable enhancements in the mechanical performance of EP/GF composite laminates by incorporation of functionalized graphene oxide (FGO) nanofiller, whilst the mechanical performance of the GO reinforced composite only improved marginally. Finally, the mechanical performance of the EP/GF/FGO multi-scale composites was found to be dependent on the type of FGO functional groups; of which EDA exhibited the highest performance. These investigations confirmed that the EDA-FGO-reinforced EP/GF composites possess excellent potential to be used as multifunctional engineering materials in industrial applications.     

Synthesis and characterization of fluorine-containing cholesteric liquid crystalline polysiloxanes bearing trifluoromethyl-substituted mesogens

A series of side-chain liquid crystal (LC) polysiloxanes were synthesised with Poly(methylhydrogeno)siloxane, 4?-(undec-10-enoyloxy) biphenyl – 4 – yl 4- (trifluoromethyl) benzoate (M_th) and a chiral nematic (N*) LC monomer 1-allyl 10-(cholesteryl)-decanedioate (M_ch). The chemical structures and LC properties of the monomers and polymers were characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, POM and X-ray diffractometer. M_ch is monotropic N* LC. The homopolymer derived from monomer M_ch is enantiotropic N* LC. Monomer M_th is a smectic A liquid crystal. The copolymers derived from M_ch and M_th are N* LCs. The temperatures at which 5% weight loss occurred are greater than 300°C for all the fluoro-containing polymers, and the residue weights of the samples at 600°C increased slightly as the content of trifluoromethyl mesogens increased in the polymers. The glass transition temperatures of the polymers increased as trifluoromethyl mesogens increased, too. The N*–I phase transition temperatures show a negative deviate from ideal or linear behaviour. The values of the enthalpy changes for the cholesteryl containing polymers are rather low and this is attributed to the biaxiality of cholesteryl moiety which tends to reduce the change in the orientational order at the N*–I transition. Compared to the monomers, the polymers show wider mesophase region.