Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

Reversible nonlinear conduction in high‐density polyethylene/acetylene carbon black composites at various ambient temperatures

The reversible nonlinear conduction (RNC) in of high‐density polyethylene/acetylene carbon black composites with different degrees of crosslinking was studied above room temperature and below the melting point of high‐density polyethylene (HDPE). The experimental current density‐electric field strength curves can be overlapped onto a master curve, suggesting that the microscopic mechanisms for the appearance of RNC exist regardless of the ambient temperature and the crosslinking degree of the HDPE matrix. The relationship between the crossover current density and the linear conductivity can be explained in the framework of the dynamic random‐resistor‐network model. According to these results, two electron‐tunneling models are suggested to interpret the microscopic conduction behavior. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1212–1217, 2004     

密封容器中后处理制备Tl2Ba2CaCu2Oy高温超导薄膜及其性能研究

以铝酸镧（001）单晶为基片，采用两步法制备Tl2Ba2CaCu2Oy（Tl 2212）高 温超导薄膜.首先，利用脉冲激光沉积（PLD）工艺沉积Ba2CaCu2Ox非晶前驱体薄膜；然后，前驱体薄膜在高温（720—850℃）下密封钢容器里铊化结晶形成Tl 2212薄膜.XRD结果表明Tl2212 薄膜是沿c轴方向生长的，其相组成为Tl 2212，摇摆曲线（0012）的半高宽为0.72° ，SEM图像显示其表面光滑平整，其零电阻温度为106.2K. 关键词： Tl 2212超导薄膜 脉冲激光沉积     

Synthesis of Cationic PEM Emulsion and Application in Waste Water Treatment

Cationic polymer as a kind of flocculant is widely applied in purification treatment of waste water. Because it has positive charge group, it is able to connect strongly the suspended matters, short cellulose and other microparticles. The research on synthesis of cationic polymer and application in treatment of waste water is very universal abroad. But domestic research on those is not general. The technology of synthesis of PEM is simple, and the production cost is low. It is easy to apply in treatment of waste water.Synthesis of PEM Emulsion FlocculantSome distilled water, PVA(poly(vinyl alcohol)), EA(ethyl acrylate), and K2S2O8(potassium persulfate) were put into reaction vessel. Kept stirring up under nitrogen. When heated the solution to 40℃, dropped the water solution of MTA[(2-methacryloxylethyl)trimethyl ammonium].Maintained the temperature at 70℃, reacted about 7-8 hours. Then got the PEM emulsion. Changed the ratio of EA and MTA. Obtained a series of PEM emulsions.Stability and Convertibility of PEM EmulsionThe test results showed that when the EA/MTA was 85/15, the PEM emulsion was most stable.When the total monomer quantity was 35%, the convertibility of PEM emulsion was the highest,i.e.98.6%.The MTA Copolymerization Ratio and Morphology of PEM EmulsionWhen the monomers EA/MTA=85/15 and total monomer quantity was 35%, the MTA copolymerization ratio of PEM emulsion was 95.15%(the highest), and the PEM emulsion was some microspheres with 100-180nm of diameter.The Test Results of PEM Emulsion in Treatment of Waste Water The PEM emulsion flocculant was applied in treatment of waste water of paper mill, and measured the precipitation time(t) and transmittancy(T). The test results were showed in table 1. The optimum value of PEM which was able to make the waste water of paper mill into clear water was 0.008%.     

The Research on Polymer Microcapsulation for Cell Technology

Microcapsulation is a technology that enwrapped the solid or liquid or some gas matter with membrane materials to form microparticles(i.e.microcapsules). The materials of microcapsule is composed of naturnal polymers or modified naturnal polymers or synthesized polymers. The water-soluble core matter can only use oil-soluble wall materials, and vice versa.Synthesized methods of polymer microcapsulesSynthesized methods with monomers as raw materialsThis kind of methods include suspension polymerization, emulsion polymerization, dispersal polymerization, precipitation polymerization,suspension condensation polymerization, dispersal condensation polymerization, deposition condensation polymerization, interface condensation polymerization, and so on.Synthesized methods with polymers as raw materialsThese methods are suspension cross-linked polymerization, coacervation phase separation,extraction with solvent evaporation, polymer deposition, polymer chelation, polymer gel,solidification of melting polymer, tray-painted ways, fluidized bed ways, and so forth.Polymer materials to synthesize microcapsules2.1. Naturnal polymer materialsThe characteristics of this kind of materials are easy to form membrane, good stability and no toxicity. The polymer materials include lipids(liposome), amyloses, proteins, plant gels, waxes, etc.2.2. Modified polymer materialsThe characteristics of these materials are little toxicity, high viscidity(viscosity), soluble salt materials. But they cannot be used in water, acidic environment and high temperature environment for a long time. The materials include all kind of derivants of celluloses.2.3. Synthesized polymer materialsThe characteristics of the materials are easy to form membrane, good stability and adjustment of membrane properties. The synthesized polymer materials include degradable polymers(PLA, PGA,PLGA, PCL, PHB, PHV, PHA, PEG, PPG and the like) and indegradable polymers(PA, PMMA,PAM, PS, PVC, PB, PE, PU, PUA, PVA and otherwise).The applications of polymer microcapsules in cell technologyThe "artificial cell" is the biological active microcapsule used in biological and medical fields.The applications of cells (including transgenic cells, the same as artificial cells) technology include several aspects as follows:3.1. Microcapsulation of artificial red cell3.2. Microcapsule of artificial cell of biological enzyme3.3. Microcapsule of artificial cell of magnetic material3.4. Microcapsule of artificial cell of active carbon3.5. Microcapsule of active biological cell     

Regioselective Synthesis of Multi-substituted Phenylselenomethyl Isoxazolines

A mild, regioselective 1, 3-dipolar cycloaddition protocol for the preparation ofphenylselenomethyl isoxazolines through substituted allyl phenyl selenides and nitrile oxides wasreported.     

One-pot Synthesis of 2, 5-Disubstituted Oxazoles Using Poly[styrene（iodosodiacetate）]

2,5-Disubstituted oxazoles were prepared conveniently by treatment of aromatic α-methyl ketones and nitriles with poly[styrene(iodosodiacetate)] in one-pot process.     

Solid Phase Synthesis of 2-Substituted 1,3-Oxazin-6-ones Using Resin-bound Cyclic Malonic Acid Ester

A facile solid phase synthesis of 2-substituted 1,3-oxazin-6-ones using polymer-supported Meldrum‘s acid has been reported. Reaction of the resin-bound cyclic malonic acid ester with triethyl orthoformate and subsequent double substitution with amide, afforded the corresponding polymer-supported acylaminomethylene cyclic malonic acid ester, which upon thermal treatment led to 1, 3-oxazin-6-ones in good yields and with high purity.     

A Novel Cardiac Glycoside from Parepigynum funingesis

From the dried aerial part ofParepigynumfuningesis Tsiang et P. T. Li (Apocynaceae),a new cardiac glucoside, named parefuningoside (1) had been isolated. Its structure was determined by means of hydrolysis and spectral analysis.     

Synthesis and Photocytotoxicity of Mono-functionalised Porphyrin with Valine Moiety

A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenyl ring was synthesized for photocytotoxicity examination in four steps, starting from regiospecific mono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Al adenocarcinona cell line was tested.