Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

Rim instability by solvent-induced dewetting

We study the condition of the occurrence of the rim instability in the solvent-induced dewetting process. Our experimental results show that the film thickness not only greatly influences the occurrence of the rim instability, but also influences the wavelength lambda as characterized by the undulation of the deformed contact line. The molecular weight of polymer does not almost influence the occurrence of the rim instability and the wavelength lambda. The wavelength lambda is proportional to the width of the rim in the rim instability region. The receding contact angle theta of polymer solutions on substrates in the dewetting process is an important factor to influence the rim instability in the solvent-induced dewetting.

Purification, sequencing and biological activity of polypeptide from velvet antler

The velvet antler polypeptide CNT14 was extracted and purified by gel filtration, ion exchange chromatography and RP C, which showed a single peak in HPLC chromatography and a single band in SDS-PAGE. The molecular weight measured by MALDI/TOF/MS spectrum was 1479. 9028. The polypeptide consisted mostly of Glu, Leu, Val, Pro. The amino acid sequence of the polypeptide was detected with ESI-MS/ MS, and the sequence was E-P-T-V-L-D-E-V-C-L-A-H-G-P. The experiments of biological activity of polypeptide CNT14 in vivo were carried out, and the results show that CNT14 has stimulant effects on the growth of rat HT22 cells. Then we produced the polypeptide CNT14 according the amino acid sequence by solid phase synthesis, confirmed the sequence of the polypeptide to be consistent with the amino acid sequence of polypeptide CNT14 which was separated from the velvet antler.

Monte Carlo simulation on symmetric ABA/AB copolymer blends in confined thin films

The effects of blend composition on morphology, order-disorder transition (ODT), and chain conformation of symmetric ABA/AB copolymer blends confined between two neutral hard walls have been investigated by lattice Monte Carlo simulation. Only lamellar structure is observed in all the simulation morphologies under thermodynamic equilibrium state, which is supported by theoretical prediction. When the composition of AB diblock copolymer (phi) increases, both lamellar spacing and the corresponding ODT temperature increase, which can be attributed to the variation of conformation distribution of the diblock and the triblock copolymer chains. In addition, both diblock and triblock copolymer, chains with bridge conformation extend dramatically in the direction parallel to the surface when the system is in ordered state. Finally, the copolymer chain conformation depends strongly on both the blend composition and the incompatibility parameter chi N.

Control led/living free-radical copolymerization of 4-(azidocarbonyl) phenyl methacrylate with methyl acrylate under Co-60 gamma-ray irradiation

A new vinyl acyl azide monomer, 4-(azidocarbonyl) phenyl methacrylate, has been synthesized and characterized by NMR and FTIR spectroscopy. The thermal stability of the new monomer has been investigated with FTIR and thermal gravimetry/differential thermal analysis (TG/DTA), and the monomer has been demonstrated to be stable below 50 degrees C in the solid state. The copolymerizations of the new monomer with methyl acrylate have been carried out at room temperature under Co-60 gamma-ray irradiation in the presence of benzyl 1-H-imidazole-1-carbodithioate. The results show that the polymerizations bear all the characteristics of controlled/living free-radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow (< 1.20), and a linear relationship existing between In([M](0)/[M]) and the polymerization time. The data from H-1 NMR and FTIR confirm that no change in the acyl azide groups has occurred in the polymerization process and that acyl azide copolymers have been obtained. The thermal stability of the polymers has also been investigated with TG/DTA and FTIR.

Crystallization behavior of poly(epsilon-caprolactone) in poly(epsilon-caprolactone) and poly(vinyl methyl ether) mixtures

The morphological development and crystallization behavior of poly(epsilon-caprolactone) (PCL) in miscible mixtures of PCL and poly(vinyl methyl ether) (PVME) were investigated by optical microscopy as a function of the mixture composition and crystallization temperature. The results indicated that the degree of crystallinity of PCL was independent of the mixture composition upon melt crystallization because the glass-transition temperatures of the mixtures were much lower than the crystallization temperature of PCL. The radii of the PCL spherulites increased linearly with time at crystallization temperatures ranging from 42 to 49 degrees C. The isothermal growth rates of PCL spherulites decreased with the amount of the amorphous PVME components in the mixtures. Accounting for the miscibility of PCL/PVME mixtures, the radial growth rates of PCL spherulites were well described by a kinetic equation involving the Flory-Huggins interaction parameter and the free energy for the nuclei formation in such a way that the theoretical calculations were in good agreement with the experimental data. From the analysis of the equilibrium melting point depression, the interaction energy density of the PVME/PCL system was calculated to be -3.95 J/cm(3).

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi-implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized.

Study on reactive extrusion processes of block copolymer

The anionic copolymerization process of styrene-buradiene (S/B) block copolymer in a closely intermeshing co-rotating twin screw extruder with butyl-lithium initiator was studied. According to the anionic copolymerization mechanism and the reactive extrusion characteristics, the mathematical models of monomer conversion, average molecular weight and fluid viscosity during the anionic copolymerization of S/B were constructed, and then the reactive extrusion process was simulated by means of the finite volume method and the uncoupled semi-implicit iterative algorithm. Finally, the influence of the feeding mixture composition on conversion was discussed. The simulated results were nearly in agreement with the experimental results.

Free radical grafting of polyethylene with vinyl monomers by reactive extrusion

The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results.

Relaxation time and conductivity of comb-like gel polymer electrolytes

Using the copolymer of acrylonitrile (AN), methyl methacrylate (MMA), and poly(ethylene glycol) methyl ether methacrylate as a backbone and poly(ethylene glycol) methyl ether (PEGME) with 1100 molecular weight as side chains, comb-like gel polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the gel copolymer electrolytes possess two glass transitions: alpha-transition and beta-transition. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T. as reference temperature. By reference to T-0 = 50 degrees C, the relation between log c, and c was found to be linear. The master curves are displaced progressively to higher frequencies as the content of plasticizer is increased. The relation between log tau(p) and the content of plasticizer is also linear.

Achieving perpendicular alignment of rigid polythiophene backbones to the substrate by using solvent-vapor treatment

The rigid backbone of the poly(3-butylthiophene) molecule adopts a perpendicular orientation with respect to the substrate by using a solvent-vapor treatment (see figure). Small and closely contacting spherulites instead of conventional whisker-like crystals are achieved. This could be utilized to improve charge-carrier mobility particularly in the direction normal to the film plane by designing and constructing thick crystalline domains in the functional layer.

Mixed ligands supported yttrium alkyl complexes: Synthesis, characterization and catalysis toward lactide polymerization

Treatment of yttrium tris(alkyl)s, Y(CH2SiMe3)(3)(THF)(2), by equimolar H(C5Me4)SiMe3(HCp') and indene (Ind-H) afforded (eta(5)-Cp')Y(CH2SiMe3)(2)(THF) (1) and (eta(5)-Ind)Y(CH2SiMe3)(2)(THF) (2) via alkane elimination, respectively. Complex 1 reacted with methoxyamino phenols, 4,6-(CH3)(2)-2-[(MeOCH2CH2)(2)-NCH2]-C6H2-OH (HL1) and 4,6-(CMe3)(2)-2-[(MeOCH2CH2)(2)-NCH2]-C6H2OH (HL2) gave mixed ligands supported alkyl complexes [(eta(5)-Cp')(L)]Y(CH2SiMe3) (3: L = L-1; 4: L = L-2). Whilst, complex 2 was treated with HL2 to yield [(eta(5)-Ind)(L-2)]Y(CH2SiMe3) (5). The molecular structures of 3 and 5 were confirmed by X-ray diffraction to be mono(alkyl)s of THF-free, adopting pyramidal and tetragonal-bipyramidal geometry, respectively. Complexes 3 and 5 were high active initiators for the ring-opening polymerization Of L-lactide to give isotactic polylactide with high molecular weight and narrow to moderate polydispersity.

Metabolic profiling of serum from gadolinium chloride-treated rats by H-1 NMR spectroscopy

Metabolic profiling of serum from gadolinium chloride (GdCl3, 10 and 50 mg/kg body weight, intraperitoneal [i.p.])-treated rats was investigated by the NMR spectroscopic-based metabonomic strategy. Serum samples were collected at 48, 96, and 168 h postdose (p.d.) after exposure to GdCl3. H-1 NMR spectra of serum were analyzed by pattern recognition using principal components analysis. The studies showed that there was a dose-related biochemical effect of GdCl3 treatment on the levels of a range of low-molecular weight compounds in serum. The liver damage induced by GdCl3 was characterized by the elevation of lactate, pyruvate, and creatine as well as the decrease of branched-chain amino acids (valine and isoleucine), alanine, glucose, and trimethylamine-N-oxide concentration in serum samples. The biochemical effects of GdCl3 in rats could be consulted when evaluating the biochemical profile of gadolinium-containing compounds that are being developed for nuclear magnetic resonance imaging.

Electron-beam irradiation on poly(propylene carbonate) in the presence of polyfunctional monomers

Poly(propylene carbonate) (PPC) showed predominantly degradation under electron-beam irradiation, accompanied by deterioration of its mechanical performance due to sharp decrease of the molecular weight. Crosslinked PPC was prepared by addition of polyfunctional monomer (PFM) to enhance the mechanical performance of PPC. When 8 wt% of PFM like triallyl isocyanurate (TAIL) was added, crosslinked PPC with a gel fraction of 60.7% was prepared at 50 kGy irradiation dose, which showed a tensile strength at 20 degrees C of 45.5 MPa, whereas it was only 38.5 MPa for pure PPC. The onset degradation temperature (T-i) and glass transition temperature (T-g) of this crosslinked PPC was 246 degrees C and 45 degrees C, respectively, a significant increase related to pure PPC of 211 degrees C and 36 C. Therefore, thermal and mechanical performances of PPC could be improved via electron-beam irradiation in the presence of suitable PFM.