Numerical Simulation of Reactive Extrusion Processes for Activated Anionic Polymerization

In order to deal with the complicated relationships among the variables of the reactive extrusion process for activated anionic polymerization, a three-dimensional equivalent model of closely intermeshing co-rotating twin screw extruders was established. Then the numerical computation expressions of the monomer concentration, the monomer conversion, the average molecular weight and the fluid viscosity were deduced, and the numerical simulation of the reactive extrusion process of Styrene was carried out. At last, our simulated results were compared with Michaeli's simulated results and experimental results. (C) 2007 Elsevier B.V. All rights reserved

Effect of the nucleating agent 1,3 : 2,4-di(3,4-dimethylbenzylidene) sorbitol on the gamma phase content of propylene/ethylene copolymer

The influence of the concentration of a nucleating agent (NA), namely 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS), on the gamma phase content in a propylene/ethylene copolymer was investigated by means of Differential Scanning Calorimetry (DSC), Wide-Angle X-ray Diffraction (WAXD), Small- Angle X-ray Scatter (SAXS) and Polarized Optical Microscopy (POM).

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

The dewetting dynamics of the polymer thin film by solvent annealing

The slippage effect of the polymer chains is investigated in the dewetting process of the polymer solution film. The solvent-induced dewetting is used in our experiments to study the dynamics of hole growth in the dewetting process of the polymer solution film. Our results show that in the case of the low molecular weight polystyrene (PS) film, the slippage effect of the polymer chains is not displayed and the radius of the holes is R similar to exp(t/tau); in the case of the higher molecular weight PS film, the slippage effect of the polymer chain is not valid in the case of the thin film and that is valid in the case of the thick film, and the dynamic process of hole growth divides into three stages (R similar to t, and then R similar to t(x) (2/3 < x < 1), finally, R similar to t). Besides, the solvent and substrate properties also influence the dewetting dynamics of the polymer solution film.

Effect of polydispersity on the self-assembly structure of diblock copolymers under various confined states: A Monte Carlo study

We studied the self-assembly of polydisperse diblock copolymers under various confined states by Monte Carlo simulation. When the copolymers were confined within two parallel walls, it was found that the ordered strip structures appeared alternately with the increase in wall width. Moreover, the wall width at which the ordered structure appeared tended to increase with an increase in the polydispersity index (PDI). On the other hand, the simulation results showed that the copolymers were likely to form ordered concentric strip structures when they were confined within a circle wall.

Effect of the nature of annealing solvent on the morphology of diblock copolymer blend thin films

The morphologies and structures for the thin film of blend systems consisting of two asymmetric polystyrene-block-polybutadiene (SB) diblock copolymers induced by annealing in the vapor of different solvents, namely, cyclohexane, benzene, and heptane, which have different selectivity or preferential affinity for a certain block, were investigated by tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results revealed that even a slight preferential affinity of good solvent for one block would strongly alter the morphology of the blend thin film.

Construction of hollow DNA/PLL microcapsule as a dual carrier for controlled delivery of DNA and drug

DNA/poly-L-lysine (PLL) capsules were constructed through a layer-by-layer (LbL) self-assembly of DNA and PLL on CaCO3 microparticles, and then used as dual carriers for DNA and drug after dissolution of carbonate cores. The permeability of DNA/PLL microcapsules was investigated with fluorescence probes with different molecular weights by confocal microscopy. The result revealed that the fluorescence probes were able to penetrate the capsule walls even its molecular weight up to 150 kDa. The resultant capsules were used to load drug model molecules-fluorescein isothiocyanate (FITC)-dextran (4 kDa) via spontaneous deposition mechanism.

Morphology and crystalline transition of poly (3-butylthiophene) associated with its polymorphic modifications

Poly (3-butylthiophene) (P3BT) is a much less studied conjugated polymer despite its high crystallizability and thus excellent electrical property. In this work, morphology of P3BT at different crystalline polymorphs and solvent/thermal induced phase transition between form I and U modifications have been intensively investigated by using optical microscopy, electron microscopy, differential scanning calorimetry, and X-ray diffraction. It is shown that a direct deposition from carbon disulfide (CS2) at fast evaporation results in P3BT crystals in form I modification, giving typical whiskerlike morphology. In contrast, low evaporation rate from CS, leads to formation of form II crystals with spherulitic morphology, which is so far scarcely observed in polythiophene.

Self-assembly of a hydrophobic polypeptide containing a short hydrophilic middle segment: Vesicles to large compound micelles

This report describes a facile route to prepare the vesicles and large compound micelles (LCMs) from a series of poly(epsilon-benzyloxycarbonyl L-lysine)-block-poly[diethylene glycol bis(3-amino propyl) ether]-block-poly(epsilon-benzyloxycarbonyl L-lySine) (PZLL-DGBE-PZLL) in their water solution, depending on molecular weight of the polypeptides. A pyrene probe is used to demonstrate the aggregate formation of PZLL-DGBE-PZLL in solution, and also to measure their critical micelle concentration as a function of molecular weight of the polymer.

Stabilization of poly(lactic acid) by polycarbodiimide

Polycarbodiimide (CDI) was used to improve the thermal stability of poly(L-lactic acid) (PLA) during processing. The properties of PLA containing various amounts of CDI were characterized by GPC, DSC, rheology, and tensile tests. The results showed that an addition of CDI in an amount of 0.1-0.7 wt% with respect to PLA led to stabilization of PLA at even 210 degrees C for up to 30 min, as evidenced by much smaller changes in molecular weight. melt viscosity, and tensile strength and elongation compared to the blank PLA samples. In order to examine the possible stabilization mechanism, CDI was reacted with water, acetic acid, L-lactic acid, ethanol and low molecular weight PLA. The molecular structures of the reaction products were measured with FTIR.

Ethylene polymerization, and the copolymerizations of ethylene with hexene or norbornene with highly active mono(beta-enaminoketonato) vanadium(III) catalysts

Five novel vanadium(III) complexes [PhN = C(R-2)CHC(R-1)O]VCl2(THF)(2) (4a: R-1 = Ph, R-2 = CF3; 4b: R-1 =t-Bu, R-2 = CF3; 4c: R-1 = CF3, R-2 = CH3; 4d: R-1 = Ph, R-2 = CH3; 4e: R-1 = Ph, R-2 = H) have been synthesized and characterized. On activation with Et2AlCl, all the complexes, in the presence of ethyl trichloroacetate (ETA) as a promoter, are highly active precatalysts for ethylene polymerization, and produce high molecular weight and linear polymers. Catalyst activities more than 16.8 kg PE/mmolv h bar and weight-average molecular weights higher than 173 kg/ mol were observed under mild conditions.