Research and synthesis of organosilicon nonthrombogenic materials containing sulfobetaine group

A novel organosilicon sulfobetaine was synthesized through the reaction of organosilicon containing tertiary amino with 1,3-propanesulfone. Then this organosilicon sulfobetaine was coated onto polyurethane and organosilicon surface to improve their blood compatibility. The existence of sulfobetaine structure on the surface of materials was revealed by ATR-FTIR and XPS. The thermo-capability of synthesized silicone rubber, containing sulfobetaine was revealed by TGA. The blood compatibilities of organosilicon sulfobetaine and other materials such as silicone and PU as reference coated with them were evaluated by platelet-rich plasma adhesion experiment. The novel segmented silicone rubber containing sulfobetaine structure showed perfect blood compatibility.     

具有生物活性的有机硅化合物研究近况

生物有机硅化合物的研究进展迅速,而且越来越受到人们的重视。实际上,它是有机硅化学的一个新的分支。本文对有机硅化合物的毒理学、有机硅药物化学以及有机硅农药作了简要的论述。     

Synthesis of silicon-carbon spiranes by metathesis on an aluminumrhenium catalyst

Dialkenyl derivatives of i-silacyclobutane and 1-silacyclopent-3-ene with double bonds - and - to the silicon atom undergo metathesis over an aluminumrhenium catalyst to give silaspirocyclic compounds and open-chain organosilicon trienes containing the silacyclobutane and silacyclopentene fragments. Metathesis of allylbutenyl derivatives of silacyclobutane and silacyclopentene provides a convenient synthetic route to 4-silaspiro[3,5]non-6-enes and 5-silaspiro[4,5]deca-2,7-dienes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2797–2803, December, 1989.     

Control of the plasticity of organosilicon rubbers by their modification with polypyrrole

Modification of organosilicon rubbers SKTN and SKTV with polypyrrole was studied. The modifying agent was synthesized directly in the rubbers containing iron trichloride acting as oxidant and catalyst, using the diffusion procedure and impregnation of organosilicon rubbers with pyrrole-2-carboxylic acid in supercritical carbon dioxide. Changes in the ductility and viscosity of the composite materials were analyzed.     

Efficient synthesis of 1,2,4-dithiazolidine-3,5-diones [dithiasuccinoyl-amines] from bis(chlorocarbonyl)disulfane plus bis(trimethylsilyl)amines

The 1,2,4-dithiazolidine-3,5-dione heterocycle, also referred to as a dithiasuccinoyl (Dts)-amine, serves as a readily removable amino protecting group for building blocks used in syntheses of peptides, glycopeptides, and PNA; it is also useful as a masked isocyanate and (inversely) as a sulfurization reagent for trivalent phosphorus. Bis(chlorocarbonyl)disulfane, the two-sulfur analogue of succinyl chloride, has been envisioned as a reagent for facile single-step elaboration of the heterocycle. However, reactions of bis(chlorocarbonyl)disulfane directly with primary amines fail to yield Dts-amines for reasons that are discussed. Inspired by several precedents from the organosilicon chemistry literature that a trimethylsilyl group may serve as a "large proton," a successful, high-yield preparation of Dts-amines through reactions of bis(chlorocarbonyl)disulfane with bis(trimethylsilyl)amines has been developed. Studies aimed at elucidating mechanistic reasons for these observations are also presented.     

Synthesis of some triphenylmethyl- and triphenylethylsiloxanes

Summary For the first time 8 pure oxygen-captaining organosilicon compounds were prepared; some of them can be utilized for the preparation of high-molecular organosilicon polymers.     

Organosilicon compounds III. Silicon-substituted thiophene derivatives of mercaptoethylamine as possible radioprotective agents

The preparation of the first organosilicon containing derivatives of mercaptoethylamine as possible radioprotective agents is described. The synthesis of these compounds via the thiazolidine intermediate was chosen due to the known radioprotective action of certain thiazolidines. We have prepared seventeen previously unreported organosilicon derivatives of which eleven contain the thiazolidine moiety and six are derivatives of mercaptoethylamine. The ability of these derivatives to protect against ionizing radiation will be determined.     

A novel insight into the inductive effect in silicon chemistry

A revision of quantitative literature data for the reactivity of organosilicon compounds in light of conceptions stemmed from organic chemistry has been carried out. It has been found that in structure-reactivity analysis for organosilicon compounds, differently of carbon compounds, the inductive effect of substituents, at least in nucleophilic displacement reactions at silicon, must be expressed by two terms involving that for electronegativity. A protocol for the correlation analysis in organosilicon chemistry is now available.     

An interpenetrated metal-organic framework and its gas storage behavior: simulation and experiment

A new metal-organic framework, called UHM-6 (UHM: University of Hamburg Materials), based on the copper paddle wheel motif and a novel organosilicon linker, 4',4″-(dimethylsilanediyl)bis(biphenyl-3,5-dicarboxylic acid) (sbbip), has been synthesized and characterized with regard to its gas storage behavior up to 1 bar for hydrogen, methane, and carbon dioxide. The 2-fold interpenetrated microporous framework of UHM-6 is isoreticular to PMOF-3 (Inorg. Chem.2009, 48, 11507) and is composed of cuboctahedral cages of Cu(2) paddle wheels connected via nonlinear organosilicon units. The structure (SG I422, No. 97) is characterized by straight channels running along the [001] and [110] direction. UHM-6 reveals a specific surface area of S(BET) ~ 1200 m(2) g(-1) and a specific micropore volume of V(micropore) ~ 0.48 cm(3) g(-1). At 1 bar the activated form of UHM-6 shows a hydrogen uptake of 1.8 wt % (77 K), a methane uptake of 0.8 mmol g(-1) (293 K), and a carbon dioxide uptake of 3.3 mmol g(-1) (273 K). Accompanying theoretical grand-canonical Monte Carlo (GCMC) simulations show an overall good agreement with the experimental results. Furthermore, GCMC adsorption simulations for three binary equimolar mixtures (CH(4)/H(2), CO(2)/H(2), and CO(2)/CH(4)) were carried out (T = 298 K) to assess the potential for gas separation/purification applications.     

有机硅参与的聚电解质的合成及性能研究

以带磺酸根离子单体，丙烯酸酯单体，丙烯酸与甲基丙烯酰氧丙基三甲氧基硅烷（MAPS）进行紫外光引发溶液聚合，研制出一种可粘在聚二甲基硅氧烷橡胶上的聚电解质。并就各个单体用量对聚合物粘接性能，离子交换当量，柔韧性等的影响进行了探讨。结果表明：采用4－乙烯基苯磺酸钠，甲基丙烯酸丁酯，丙烯酸和甲基丙烯酰氧丙基三甲氧基硅烷在紫外光引发下聚合1h，常温固化可得到满足要求的聚电解质。     

Insecticidal potency of certain organosilicon compounds

A small series of organosilicon compounds were screened for efficacy against the housefly Musca domestica. The activity of organosilicon compounds is attributed to the silicon atom, the presence of halogens and the alkyl groups.     

有机硅-丙烯酸酯聚合物乳液合成及粒径分析

通过种子乳液半连续法合成了有机硅改性丙烯酸酯聚合物乳液,并对其粒子形态及分布进行分析。结果表明:通过种子乳液半连续聚合工艺可制备出固含量42wt%,乳化剂含量4wt%(基于单体量)、窄分布纳米粒子的有机硅改性丙烯酸酯聚合物乳液。随反应进行,粒径分布变窄,平均粒径逐渐增大。随乳化剂中SDS与OP-10的摩尔比减少,粒径增大。     

Organosilicon ion‐exchange and complexing adsorbents

Literature data concerning research organosilicon ion‐exchangers and complexing agents have been summarized and systematized. Data on organophilic organosilicon adsorbents and sorption systems for chromatography are not considered here. Copyright © 1999 John Wiley & Sons, Ltd.     

Carbon-reinforced plastics based on hybrid polyimide-organosilicon binders

Compounds based on the synthesized polyimides and organosilicon resins were developed. The compatibility of organosilicon resins with polyimide binders was studied by electron microscopy. The possibility of preparing fibrous composite materials, carbon-reinforced plastics, using such polyimide-organosilicon binders was demonstrated. The viscoelastic and strength properties of the materials obtained were studied. The optimum binder composition, ensuring 90% preservation of the elastic modulus and 70% preservation of strength of the carbon-reinforced plastic relative to the initial values after keeping in air for 50 h at 350°C, was chosen.     

The influence of an organosilicon modifier on the properties of a compound based on epoxy-urethane oligomer

To improve the performance characteristics of products made of highly-filled polymer compositions, modification of a compound based on epoxy-urethane oligomer was performed. The SH 198 amino functional organosilicon oligomer was used as a modifier. The performed studies established that an organosilicon modifier increases the gel time and the curing time of the composition based on epoxy-urethane oligomer, shows the plasticizing effect on a compound, decreases its glass transition temperature from 16.5 to 9°C, and increases the deformation in the temperature range of from–40 to +50°C.     

Rubbers with low flammability

Ways to decrease the flammability of rubber materials based on organosilicon rubbers of different structures and on ethylene–propylene–diene rubbers are shown. Data on the influence of the structure of organosilicon rubbers on their flammability and the influence of metal hydroxides and their dispersion on the decrease in the flammability of rubbers are given.     

某些新的氟代有机硅化合物的合成

本文用含硅氢键化合物与含双键的氟化合物的加成反应,制备了一系列未见报导的含氟有机硅化合物。在用氯丙烯与2,2,3,3-四氟丙醇制2,2,3,3-四氟丙基烯丙醚时,对方法进行了改进,提高了产率。本文还报道了含氟有机硅聚合物方面的工作。     

Heterophase polymerization of styrene in the presence of organosilicon compounds of various natures

The heterophase polymerization of styrene has been carried out in the presence of surfactants—organosilicon compounds with different solubilities in aqueous and styrene phases and surface activities at the interface. It has been demonstrated that the stability of polymer suspensions prepared with water-insoluble organosilicon compounds is much higher than that in the presence of organosilicon surfactants soluble in organic and aqueous phases. In the former case, suspensions with narrower particle-size distributions are produced. The stability of polymer microspheres prepared at various monomer-to-water volume ratios has been tested. An increase in the monomer concentration above 25 vol % leads to the loss of system stability.     

The synthesis of organosilicon diacetylene alcohols with conjugate tertiary bonds

Summary A method was developed for obtaining organosilicon diacetylene alcohols with conjugate tertiary bonds.     

Organosilicon sonochemistry

Sonochemical reactions involving organosilicon compounds are reviewed. Possible applications of ultrasonic irradiation for acceleration and initiation of various types of reactions are demonstrated along with examples from organic synthesis using organosilicon compounds. Also described are the sonochemical reactions of organic compounds containing the Group IVB elements germanium and tin, chemically related to silicon.