SYNTHESIS OF POLYSUBSTITUTED AROMATIC COMPOUNDS：2．THE DIELS－ALDER REACTION OF 1－CHLORO SUBSTITUTED DIENES WITH DIMETHYL ACETYLENEDICARBOXYLATE

ＳＹＮＴＨＥＳＩＳＯＦＰＯＬＹＳＵＢＳＴＩＴＵＴＥＤＡＲＯＭＡＴＩＣＣＯＭＰＯＵＮＤＳ：２ＴＨＥＤＩＥＬＳ－ＡＬＤＥＲＲＥＡＣＴＩＯＮＯＦ１－ＣＨＬＯＲＯＳＵＢＳＴＩＴＵＴＥＤＤＩＥＮＥＳＷＩＴＨＤＩＭＥＴＨＹＬＡＣＥＴＹＬＥＮＥＤＩＣＡＲＢＯＸＹＬ...     

MOLECULAR MECHANICAL AND QUANTUM CHEMICAL CALCULATION ON ACYLATION REACTIVITY FOR 1－（NITRO SUBSTITUTED ANILINO）－4－SUBSTITUTED－2，6－PIPERAZINEDIONES

ＭＯＬＥＣＵＬＡＲＭＥＣＨＡＮＩＣＡＬＡＮＤＱＵＡＮＴＵＭＣＨＥＭＩＣＡＬＣＡＬＣＵＬＡＴＩＯＮＯＮＡＣＹＬＡＴＩＯＮＲＥＡＣＴＩＶＩＴＹＦＯＲ１－（ＮＩＴＲＯＳＵＢＳＴＩＴＵＴＥＤＡＮＩＬＩＮＯ）－４－ＳＵＢＳＴＩＴＵＴＥＤ－２，６－ＰＩＰＥＲＡＺ...     

FLUORESCENCE STUDIES ON SELF－ASSEMBLING BEHAVIOR OF AMPHIPHILES WITH NAPHALENE－1，5－DIOXY GROUP

ＦＬＵＯＲＥＳＣＥＮＣＥ　ＳＴＵＤＩＥＳ　ＯＮ　ＳＥＬＦ－ＡＳＳＥＭＢＬＩＮＧ　ＢＥＨＡＶＩＯＲ　ＯＦ　ＡＭＰＨＩＰＨＩＬＥＳ　ＷＩＴＨ　ＮＡＰＨＡＬＥＮＥ－１，５－ＤＩＯＸＹ　ＧＲＯＵＰＦＬＵＯＲＥＳＣＥＮＣＥＳＴＵＤＩＥＳＯＮＳＥＬＦ－ＡＳＳＥＭ...     

SYNTHESIS AND X－RAY STRUCTURE OF A NEW PYRRYL SUBSTITUTED PHOTOCHROMIC FULGIDE

ＳＹＮＴＨＥＳＩＳＡＮＤＸ－ＲＡＹＳＴＲＵＣＴＵＲＥＯＦＡＮＥＷＰＹＲＲＹＬＳＵＢＳＴＩＴＵＴＥＤＰＨＯＴＯＣＨＲＯＭＩＣＦＵＬＧＩＤＥＳＹＮＴＨＥＳＩＳＡＮＤＸ－ＲＡＹＳＴＲＵＣＴＵＲＥＯＦＡＮＥＷＰＹＲＲＹＬＳＵＢＳＴＩＴＵＴＥＤＰＨＯＴＯＣＨＲ...     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

RUTHENIUM COORDINATION COMPOUNDS WITH POLYPYRIDINES V．DNA－BINDING STUDIES OF Ru（Ⅱ）COORDINATION COMPOUNDS WITH（2－PHENYL－）IMIDAZO［f］1，10－PHENANTHROLINE

ＲＵＴＨＥＮＩＵＭＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨＰＯＬＹＰＹＲＩＤＩＮＥＳＶ．ＤＮＡ－ＢＩＮＤＩＮＧＳＴＵＤＩＥＳＯＦＲｕ（Ⅱ）ＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨ（２－ＰＨＥＮＹＬ－）ＩＭＩＤＡＺＯ［ｆ］１，１０－...     

PREPARATION OF HETEROBIMETALLIC COMPLEXES BRIDGING WITH π，π－BOUND PHENYLCYCLOPENTADIENYL LIGAND AND X－RAY CRYSTAL STRUCTURE OF （TRICARBONYL－π－CHROMIUM）PHENYLCYCLOPENTADIENYLCOBALT DICARBONYL

ＰＲＥＰＡＲＡＴＩＯＮＯＦＨＥＴＥＲＯＢＩＭＥＴＡＬＬＩＣＣＯＭＰＬＥＸＥＳＢＲＩＤＧＩＮＧＷＩＴＨπ，π－ＢＯＵＮＤＰＨＥＮＹＬＣＹＣＬＯＰＥＮＴＡＤＩＥＮＹＬＬＩＧＡＮＤＡＮＤＸ－ＲＡＹＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＯＦ（ＴＲＩＣＡＲＢＯＮＹＬ...     

STUDIES ON CHIRAL THIOPHOSPHORIC ACIDS AND THEIR DERIVATIVES 13．THE ASYMMETRIC CYCLIZATION OF （＋）－SUBSTITUTED CYCLOPENTANODIAMINE WITH O－ARYL THIOPHOSPHOROCHLORIDATES

ＳＴＵＤＩＥＳＯＮＣＨＩＲＡＬＴＨＩＯＰＨＯＳＰＨＯＲＩＣＡＣＩＤＳＡＮＤＴＨＥＩＲＤＥＲＩＶＡＴＩＶＥＳ１３．ＴＨＥＡＳＹＭＭＥＴＲＩＣＣＹＣＬＩＺＡＴＩＯＮＯＦ（＋）－ＳＵＢＳＴＩＴＵＴＥＤＣＹＣＬＯＰＥＮＴＡＮＯＤＩＡＭＩＮＥＷＩＴＨＯ－ＡＲＹ...     

STUDIES ON THE NON－ISOTHERMAL KINETICS OF THERMAL DECOMPOSITIONS OF THE COMPLEXES OF Cd（II）WITH O－VANILLIN THIOSEMICARBAZONE AND IRON（III）WITH 2－［（O－HYDROXYBENZYLIDENE）AMINO］PHENOL AND PYRIDINE

ＳＴＵＤＩＥＳＯＮＴＨＥＮＯＮ－ＩＳＯＴＨＥＲＭＡＬＫＩＮＥＴＩＣＳＯＦＴＨＥＲＭＡＬＤＥＣＯＭＰＯＳＩＴＩＯＮＳＯＦＴＨＥＣＯＭＰＬＥＸＥＳＯＦＣｄ（ＩＩ）ＷＩＴＨＯ－ＶＡＮＩＬＬＩＮＴＨＩＯＳＥＭＩＣＡＲＢＡＺＯＮＥＡＮＤＩＲＯＮ（ＩＩＩ）ＷＩＴ...     

STUDY ON THE SORPTION BEHAVIOR OF N－METHYL－2－THIO－IMIDAZOLE RESIN FOR Rh（Ⅲ）AND SEPARATION OF Rh（Ⅲ）WITH COMMON METAL IONS BY USING MTIR

ＳＴＵＤＹＯＮＴＨＥＳＯＲＰＴＩＯＮＢＥＨＡＶＩＯＲＯＦＮ－ＭＥＴＨＹＬ－２－ＴＨＩＯ－ＩＭＩＤＡＺＯＬＥＲＥＳＩＮＦＯＲＲｈ（Ⅲ）ＡＮＤＳＥＰＡＲＡＴＩＯＮＯＦＲｈ（Ⅲ）ＷＩＴＨＣＯＭＭＯＮＭＥＴＡＬＩＯＮＳＢＹＵＳＩＮＧＭＴＩＲＣｈｅｎＹｉｙｏｎ...     

含苯并氮杂15-冠-5侧基的线型聚硅氧烷促进液膜离子传输性能

N-十一碳烯和N-烯丙基苯并氮杂15-冠-5和甲基二氯硅烷硅氢加成后, 再与端羟基聚二甲基硅氧烷反应, 用三甲基氯硅烷封端, 合成了两种含苯并氮杂15-冠-5侧基的线型聚硅氧烷。分别以两种聚合物为液膜离子传输载体, 研究了载体种类、阴离子、阳离子种类及载体浓度和盐浓度对离子传输速率的影响, 并考察了膜的稳定性。     

Influence of side chains assembly on the structure and transport properties of comb-like polysiloxanes in hydrocarbon separation

We have synthesized a number of comb-like polysiloxanes with linear, branched, cyclic and silicon-containing substituents; most of them are new and previously not studied polymers. The physicochemical properties of comb-like polysiloxanes have been systematically investigated. Differential-scanning calorimetry and wide-angle X-ray scattering data revealed the side-chain microphase assembly for polymers with linear aliphatic substituents, while the polymers with bulky substituents did not form a microphase. It is shown that the ratio of microphase in the polymer is greater, the closer the values of the thickness of the microphase layer and the length of the cross-link. The effect of the side-chain substituent on the hydrocarbon transport properties of comb-like polysiloxanes was studied. All synthesized polymers are promising as membrane materials for a vital process of hydrocarbon separation. This is associated with an increase in the solubility selectivity of n-butane/methane because the solubility coefficient of methane sharply decreases when long side chains are introduced into the polysiloxane. It was shown for the first time that microphase forming polymers have a significantly higher butane/methane selectivity (23.2–27.5) than polysiloxanes not forming a microphase (selectivity 12.3–20.0). The effect is demonstrated on polysiloxanes with various types of side substituents. It was revealed that for the comb-like polysiloxanes, the diffusivity selectivity and permselectivity are proportional to the fraction of the side-chain microphase in the polymer. With the increase in the hydrocarbon microphase share, the diffusion coefficient of the permanent gas methane is decreasing more rapidly than n-butane, which dissolves well in hydrocarbons and plasticizes polymer. Consequently, the polymers forming the microphase have a higher selectivity C₃₊/CH₄ in the separation of a multicomponent hydrocarbons mixture.     

聚硼硅氧烷的制备及应用研究进展

聚硼硅氧烷作为元素改性聚硅氧烷中的一类新型有机高分子材料,它是将硼元素引入聚硅氧烷的硅氧骨架中而得到聚合物,较普通的有机聚硅氧烷有更优异的耐高温性和粘接性能,因而具有更为广阔的应用前景。本文就近几十年来聚硼硅氧烷的合成方法进行了综述,并简单介绍了聚硼硅氧烷的性能及其作为耐高温胶粘剂、耐热阻燃剂、耐热涂料、硅硼碳氧陶瓷前驱体等材料方面的应用状况。     

Synthesis of linear and hyperbranched sugar‐grafted polysiloxanes using N‐hydroxysuccinimide‐activated esters

A straightforward method for the preparation of polysiloxanes grafted with carbohydrate side groups is described. Two kinds of backbones have been functionalized, namely one‐dimensional, linear polysiloxanes, and hyperbranched poly(siloxysilane)s based on cyclotetrasiloxanes. The method enables us to keep a good integrity of the polysiloxane backbone. The introduction of intermediate activated esters as side groups on the polysiloxane backbone ensures a complete homogeneity of the reaction medium during sugar grafting in dimethyl sulfoxide, and consequently an easy grafting with the unprotected amino sugar. Solubility of the resulting polysiloxanes has been tested in various solvents. The sugar‐grafted polysiloxanes are good candidates for applications such as silicone formulations, hydrophilic silicone elastomers, interactions with metallic nanoparticles, and suspension stabilization, or as starting point for the design of more complex polysiloxanes for molecular recognition. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3607–3618     

Synthesis and ionic conductivity of mixed substituted polysiloxanes with oligoethyleneoxy and cyclic carbonate substituents

New comb polysiloxanes with mixed substituents were synthesized by hydrosilylation of PMHS with 4-allyloxymethyl-[1,3]dioxolan-2-one and tri(ethylene glycol) allyl methyl ether (AMPEO₃). The effect of the incorporation of carbonate groups on ionic transport, viscosity and thermal properties has been investigated. When doped with lithium bis(trifluorosulfonyl) imide, LiTFSI, the mixed substituted polysiloxane polymers with varying carbonate content all exhibited conductivity higher than those for the polysiloxanes with pure carbonate or pure oligoethyleneoxy substituents. The maximum ambient conductivity in this series was 1.62× 10⁻⁴ S/cm, occurring for the polymer containing 8.5% polar carbonate groups at a doping level of EO/LiTFSI = 15. The impedance measurement results showed that polymers containing larger amounts of carbonate groups exhibited lower conductivity, probably because of their increased viscosity and higher glass transition temperature. The conduction mechanism for these new comb polymers obeys free volume theory, as indicated by conductivity data fit to the VTF equation. We dedicate this paper to Professor Dick Jones, polysilane pioneer and valued friend.     

含环氧基聚硅氧烷的研究进展

含环氧基聚硅氧烷作为一类新型的功能高人子近年来受到了人们的关注。着重介绍含环氧基聚硅烷的种类、制备方法、性能特点等。     

The synthesis of novel polysiloxanes with pendant hand-basket type calix[6]crowns and their transporting properties for metal ions in a liquid membrane

Two novel polysiloxanes with pendant hand-basket type calix[6]-1,3-crown-3 and calix[6]-1,4-crown-4 were prepared by hydrosilylation of p-tert-butylcalix[6]-(2′-allyloxymethyl)-1,3-crown-3 (CA[6]C3) and p-tert-butylcalix[6]-[2′-(ω″-undecenyloxymethyl)]-1,4-crown-4 (CA[6]C4) followed by condensation reaction with silanol-terminated polydimethylsiloxane. The monomeric calix[6]crowns and two calix[6]crown-based polysiloxanes were used as carriers in a bulk membrane. All carriers showed the transport rate of the cations decreased in the order Li⁺ < Na⁺ < K⁺. The flux of K⁺ for the monomeric calix[6]crown was higher than that for polymeric carrier. In comparison with other carriers, the transport rate of calix[6]crown-4-functionalized polysiloxanes (CA[6]C4PS) towards cesium ions were increased greatly. Competitive transport experiments known to be more useful in industrial fields also revealed to give high cesium transfer rate.     

Stationary phases for gas chromatography; chemical stability of polysiloxanes

A number of polysiloxanes have been shown to be sensitive to acids when dissolved in chloroform. At 26O°C polysiloxanes were found to degrade under the influence of several compounds used or produced during the preparation of glass capillary columns.     

29Si N.M.R. investigations of polysiloxanes

A number of side chain liquid crystal polysiloxanes prepared from both homo-and co-polymeric backbones have been studied by ²⁹Si N.M.R. and the chemical shifts assigned. Partly mesogenated poly(hydrogenmethylsiloxanes) have been similarly studied and chemical shift assignments made for sequence distributions. The data should prove helpful in studies of compositional variation in preparations of side chain copolymeric polysiloxanes.     

Thermal treatment for immobilization of chiral polysiloxanes in capillary gas chromatography

The chiral selector L -t-leucine-t-butylamide has been anchored to a polysiloxane by nucleophilic displacement of 2,2,2-trifluoroethyl ester-functionalized block polysiloxanes with L -t-leucine-t-butylamide. Attempts were made to immobilize the chiral polysiloxanes inside the capillaries by thermal treatment at 300°C for 30–90 min. The polysiloxanes were found to be more resistant than Chirasil-Val to the racemization caused by such high temperature treatment. Capillary columns coated with this type of immobilized polysiloxane have shown very high enantioselectivity and thermal stability.