氯铂酸催化剂在聚碳硅烷与二乙烯基苯交联中的应用

为了提高聚碳硅烷与二乙烯基苯(polycarbosilane/divinylbenzene,PCS/DVB)硅氢化交联反应程度,采用改性氯铂酸催化的方法对PCS/DVB交联进行了研究。研究表明:氯铂酸催化性能与其用量、交联温度、以及PCS相对分子量有关。当固体PCS相对分子量低于1500,该反应中氯铂酸催化剂的用量为12.5×10-6,低分子量PCS中Si—H含量较高,且分子链支化程度低,易发生硅氢化反应;高分子量PCS中Si—H含量较低,且分子链自身支化程度高,活性基团被包裹于大分子链中,其Si—H键参加反应空间位阻大。氯铂酸催化剂在低温下催化作用不明显,催化交联的反应温度在150℃以上。

酰胺化反应制备聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)共聚物

文中以十二碳二元胺(DDMD)和聚对苯二甲酸乙二醇酯(PET)为原料,环丁砜为溶剂,制备了聚(对苯二甲酰十二碳二元胺-共-对苯二甲酸乙二醇酯)(Poly(12T-co-ET))共聚物。考察了反应温度、投料比和溶剂用量对产物相对黏度和转化率的影响,确定其最佳工艺条件为,反应温度为210°C、DDMD与PET的投料摩尔比为1.1:1、PET与溶剂的质量比为1:10,得到产物的相对黏度为1.37、转化率为82.1%。通过傅里叶变换红外光谱和核磁共振氢谱确认了产物的结构。差示扫描量热分析和热失重分析结果表明,产物的熔点为234°C、结晶温度为201°C,初始热分解温度为357°C。拉伸强度为37.0 MPa、断裂伸长率为9.32%、弯曲强度为49.2 MPa、缺口冲击强度为1.5 kJ/m^(2)。动态力学热分析结果显示其玻璃化转变温度(T_(g))为91°C。尽管共聚物的综合性能较差,但仍可以作为基体树脂进行共混改性使用,同时,该聚合方法对PET的回收和环境保护具有一定的实用价值。

聚合物热解合成类金刚石薄膜的结构及摩擦学性能研究

合成了一种新型的碳基阶梯聚合物——聚碳苯ＣＣｎ，将其涂于氮化硅陶瓷上，在常压、惰性气氛条件下经１０００～１２００℃热处理，在氮化硅底材上合成出类金刚石薄膜．利用扫描电子显微镜、喇曼光谱和Ｘ射线衍射等技术对类金刚石薄膜的表面形貌和结构进行了分析，并且对其摩擦学性能进行了考察．结果表明：类金刚石薄膜是由金刚石、石墨碳等相组成，具有较高的硬度、较低的摩擦系数和良好的耐磨损性能．

Synthesis of poly(m-phenylenediamine) with improved properties and superior prospect for Cr(VI) removal

Chemically oxidative polymerization of m-phenylenediamine was improved through adding the weak alkaline, Na2CO3. Results show that the poly （m-phenylenediamine） （PmPD） possesses a weak solubility in acidic solution according to total organic carbon （TOC） that the TOC is less than 8 mg/L, which is much lower than the discharge standard （20 mg/L）. The TOC of the PmPD synthesized with NaOH can be as high as 120.9 mg/L. This very weak solubility of PmPD synthesized with Na2CO3 facilitates its application in water purification. The oxidation state of PmPD is decreased and the yield is increased with a maximum of 84%, promoting the concentration of Na2CO3 in the synthesis. Moreover, the Cr（VI） performance of PmPD was marvelously enhanced with Na2CO3 to improve the synthesis. The largest Cr（VI） adsorbance can reach as high as 666.8 mg/g, which is far more than the performance of other common adsorbents.

Electrochemical Behavior and Specific Capacitance of Polyaniline/Silver Nanoparticle/Multi-walled Carbon Nanotube Composites

In this work, we fabricated the polyaniline/silver nanoparticle/multi-walled carbon nanotube （PANI/Ag/MWCNT） composites by in situ polymerization of aniline on the wall of Ag/MWCNTs with different aniline to Ag/MWCNT mass ratios. The chemical structure of the ternary composites was characterized by Fourier transform infrared spectroscopy, Xray diffraction, and X-ray photoelectron spectroscopy. Scanning electron microscope and high-resolution transmission electron microscopy were used to observe the morphology of the ternary composites. The results showed that the polyaniline PANI layer was prepared successfully and it covered Ag/MWCNTs completely. In addition, Ag nanoparticles between the MWCNT core and the PANI layer existed in the form of elemental crystal, which could contribute to the electrochemical performance of the composites. Then we prepared the composite electrodes and studied their electrochemical behaviors in 1 mol/L KOH. It was found that these composite electrodes had very low impedance, and exhibited lower resistance, higher electrochemical activity, and better cyclic stability compared with pure PANI electrode. Particularly, when the mass ratio of aniline to Ag/MWCNTs was 5：5, the composite electrode displayed a small equivalent series resistance （0.23 Ω） and low interfacial charge transfer resistance （〈0.25 Ω）, as well as 160 F/g of the maximum specific capacitance at a current density of 0.25 A/g in KOH solution. We could conclude that the composite material had potential applications as cathode materials for lithium batteries and supercapacitors.

Prediction of Phase Behavior for Styrene/CO2/Polystyrene Mixtures

A lattice fluid model, Sanchez-Lacombe equation, is used to predict the phase behavior for a styrene/CO2/polystyrene ternary sys-tem. The binary parameters involved in the equation were optimized using experimental data. Phase diagrams and the distribution coefficients of styrene between polymer phase and fluid phase are obtained over a wide range of pressure, temperature and composition. The analysis of ter-nary phase diagrams indicates that this system at relatively high pressure or low temperature may display two-phase equilibrium, and at low pressures or high temperatures three-phase equilibrium may appear. The distribution coefficients of styrene between the fluid phase and the polymer phase increase asymptotically to unity when the concentration of styrene increases. The results provide thermodynamic knowledge for further exploitation of supercritical carbon dioxide assisted devolatilization and impregnation.

Fast electron transfer and enhanced visible light photocatalytic activity by using poly-o-phenylenediamine modified AgCl/g-C_3N_4 nanosheets

Exfoliation of bulk graphitic carbon nitride(g‐C3N4)into two‐dimensional(2D)nanosheets is one of the effective strategies to improve its photocatalytic properties so that the 2D g‐C3N4 nanosheets(CN)have larger specific surface areas and more reaction sites.In addition,poly‐o‐phenylenediamine(PoPD)can improve the electrical conductivity and photocatalytic activity of semiconductor materials.Here,the novel efficient composite PoPD/AgCl/g‐C3N4 nanosheets was first synthesized by a precipitation reaction and the photoinitiated polymerization approach.The obtained photocatalysts have larger specific surface areas and could achieve better visible‐light response.However,silver chloride(AgCl)is susceptible to agglomeration and photocorrosion.The PoPD/AgCl/CN composite exhibits an extremely high photocurrent density,which is three times that of CN.Obviously enhanced photocatalytic activities of PoPD/AgCl/g‐C3N4 are revealed through the photodegradation of tetracycline.The stability of PoPD/AgCl/CN is demonstrated based on four cycles of experiments that reveal that the degradation rate only decreases slightly.Furthermore,.O2^-and h+are the main active species,which are confirmed through a trapping experiment and ESR spin‐trap technique.Therefore,the prepared PoPD/AgCl/CN can be considered as a stable photocatalyst,in which PoPD is added as a charge carrier and acts a photosensitive protective layer on the surface of the AgCl particles.This provides a new technology for preparing highly stable composite photocatalysts that can effectively deal with environmental issues.

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.

Dynamic Supercritical Fluid Devolatilization of Polymers

A number of studies have been reported on the applications of supercritical fluids to polymeric processes. The presence of volatiles can affect the end-use properties of polymer materials. Therefore, these volatiles must be reduced to a level below the maximum permissible limit. Conventional heat-relevant techniques for polymer devolatilization sometimes have limited effectiveness. Devolatilization with supercritical fluids, however, can enhance removal of volatiles from polymers. A model for diffusion-limited extraction is used to characterize dynamic supercritical fluid devolatilization of spherical polymer particles. The rate of supercritical fluid devolailization for styrene/polystyrene system is measured at 343 K and 18 MPa and at CO2 flow rate of 1.93, 3.27 and 5.62 L·min^-1, respectively. The model analysis, which is consistent with experimental results, indicates that the supercritical fluid devolatilization is not solubility-limited but diffusion-limited when CO2 flow rate is above 4.00 L·min^-1.

Synthesis of Polyketone STCO Promoted by Rare Earth Catalyst

To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copolymerization of carbon monoxide （CO） and styrene （ST） to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2＇-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1 ,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectroscopy respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copolymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copolymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/（mol·h）.

One-step synthesis of graphitic carbon nitride nanosheets for efficient catalysis of phenol removal under visible light

Graphitic carbon nitride(g‐C3N4)nanosheet photocatalysts were synthesized via a facile impregnation‐thermal method.The as‐prepared materials were characterized and investigated as metal‐free photocatalysts for the degradation of phenol in aqueous solution under visible light.Results revealed that the g‐C3N4nanosheets exhibited a78.9%degradation for phenol after30min,which was much faster than that of the pristine g‐C3N4.Using Brunauer‐Emmett‐Teller theory,the surface area of g‐C3N4nanosheets was103.24m2/g,which was much larger than that of g‐C3N4.The larger surface area increases the contact area of the material with phenol,enhancing the photocatalytic activity.These results highlight the potential application of sustainable metal‐free photocatalysts in water purification.

Porosity of polystyrene membranes prepared by supercritical CO2-induced phase inversion

Microporous asymmetric polystyrene （PS） membranes were prepared by supercritical CO2-induced phase inversion. The effects of different process parameters, such as temperature, COe pressure and PS concentration in casting solution, on the membrane morphologies, pore size distribution and especially on the porosity of the membranes were experimentally investigated. The porosity showed a tendency of increasing to a maximum and then decreasing with an increase of temperature, CO2 pressure or PS concentration. The effects of process parameters on the membrane porosity were explained based on the properties of supercritical fluids.

Growth and Chemical Thermodynamics Analysis of SiC Film on Si Substrate by Heating Polystyrene/Silica Bilayer Method

SiC films were prepared by modified heating polystyrene/silica bilayer method on Si（111） substrate in normal pressure flowing Ar ambient at 1300℃ . The films were investigated by Fourier transform infrared absorption, X-ray diffraction, and scanning electron microscopy measurements. The chemical thermodynamics process is discussed. The whole reaction can be separated into four steps. The carburizing of SiO is the key step of whole reaction. The main reaction-sequence is figured out based on Gibbs free energy and equilibrium constant. Flowing Ar is necessary to continue the progress of whole reaction by means of carrying out accumulating gaseous resultants. The film is very useful for application in a variety of MOS-based devices for its silica/SiC/Si（111） structure, in which the silica layer can be removed thoroughly by the standard RCA cleaning process.

Crystallization of calcium carbonate in hydrogels in presence of meso-tetrakis (4-hydroxylphenyl) porphyrin

Organic matrices play an important role in biomineralization process. In order to explore the effect of both meso-tetrakis (4-hydroxylphenyl) porphyrin (THPP) and hydrogels on calcium carbonate mineralization,and consequently synthesize functional materials based on porphyrin and calcium carbonate with tunable shapes and optical properties,a new kind of biomimetic mineralization system which combined THPP with three biopolymer hydrogels (gelatin,agarose and calcium alginate gels) was designed and investigated. A carbonate diffusion method based on the generation of CO2 by slow decomposition of ammonium hydrogen carbonate was adopted for calcium carbonate crystallization. The results show that both gelatin and alginate hydrogels exhibit the ability of stabilizing vaterite,while agarose only induces the formation of calcite. With participation of THPP in the mineralization environments,calcite is favored in all these hydrogels,while the crystal morphologies are greatly different from each other. These results indicate the perspective of THPP in regulating calcium carbonate crystallization and also provide a new strategy for fabricating advanced functional materials with controlled morphology and tunable optical properties based on calcium carbonate and THPP.

Eutectic effect during mesophase formation in co-carbonization of ethylene tar pitch and polystyrene

Ethylene tar pitch was co-carbonized with waste polystyrene to prepare mesophase pitch. The character- istics of mesophase pitches were examined using polarized light optical microscopy, apparent viscome- try, Fourier transform infrared spectrometry, IH nuclear magnetic resonance spectrometry, and X-ray diffractometry. The properties of the mesophase pitch were greatly improved because of the eutectic effect. The soluble content increased from 5% to 56%, the mesophase itself increased from 32% to 100%, and the optical texture was changed from a coarse mosaic into a flow domain after the waste polystyrene was added to the ethylene tar pitch. The apparent viscosity showed that the mesophase pitch changed from thixotropic to Newtonian suggesting improved rheological behavior during co-carbonization）The increased number of alkyl groups, which are mainly methylene groups, altered the molecular structure of the mesophase pitch in a way that resulted in the eutectic effect.

Low-temperature solution process for preparing flexible transparent carbon nanotube film for use in flexible supercapacitors

Single-walled carbon nanotubes （SWNTs） possess high conductivity, mechanical strength, transparency, and flexibility, and are thus suitable for use in flexible electronics, transparent electrodes, and energy-storage and energy-harvesting applications. However, to exploit these properties, SWNTs must be de-bundled in a surfactant solution to permit processing and use. We report a new method to prepare a SWNT-based transparent conducting film （TCF） using the diazo dye 3,3＇-（[1,1＇-biphenyl]-4,4＇-diyl）bis（4-amino naphthalene-1-sulfonic acid）, commonly known as Congo red （CR）, as a dispersant. Uniform 20-nm-thick TCFs were prepared on rigid glass and flexible polyethylene terephthalate （PET） substrates. The CR-SWNT dispersion and the CR-SWNT TCFs were characterized via UV-Vis-NIR, Raman spectroscopy, FT-IR spectroscopy, transmission electron microscopy （TEM）, field-emission scanning electron microscopy （FE-SEM） and dynamic light scattering （DLS） measurements. The sheet resistivity of the CRSWNT TCF was -34 ±6.6 Ω/□ with a transmittance of 81% at 550 nm, comparable to that of indium tin oxide-based films. Unlike SWNT dispersions prepared in common surfactants, such as sodium dodecyl sulfate （SDS）, sodium cholate （SC）, and Triton X-100, the CR-SWNT dispersion was amenable to forming TCF by drop coating. The CR-SWNT TCF was also very stable, maintaining a very low sheet resistivity even after 1,000 consecutive bending cycles of 8 mm bending radius. Further, manganese dioxide （MnO2） was electrochemically deposited on the CR-SWNT-PET film （MnO2-CR-SWNT-PET）. The as-prepared MnO2- CR-SWNT-PET electrode exhibited high specific capacitance and bendability, demonstrating promise as a candidate electrode material for flexible supercapacitors.

Nitrogen-doped carbon nanotube/polyaniline composite:Synthesis, characterization, and its application to the detection of dopamine

Nitrogen-doped carbon nanotubes (N-CNTs)/polyaniline (PANI) composites are developed as an electrode material for biosensors. The morphology, composition, and optical properties of the resulting products were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and ultraviolet-visible absorption spectra (UV-vis). Furthermore, N-CNTs/PANI composite was immobilized on the surface of a glassy carbon electrode (GCE) and applied to construct a sensor. The obtained N-CNTs/PANI-modified GCE showed one pair of redox peaks and high catalytic activity for the oxidation of dopamine (DA) in a neutral environment. Differential pulse voltam-mograms results illustrate that the fabricated DA biosensor has high anti-interference ability towards ascorbic acid (AA). In addition, the fabricated biosensor showed superior performances with two wide linear ranges from 1 to 80 μM and from 1.5 to 3.5 mM and a low detection limit of 0.01 μM.