Synthesis of isotactic polystyrene with a rare-earth catalyst

Polymerization of styrene with the neodymium phosphonate Nd(P-507)/H2O/Al(i-Bu)(3) catalytic system has been examined. The polymer obtained was separated into a soluble and an insoluble fraction by 2-butanone extraction. C-13-NMR spectra indicate that the insoluble fraction is isotactic polystyrene and the soluble one is syndiotactic-rich atactic polystyrene. The polymerization features are described and discussed. The optimum conditions for the polymerization are as follows: [Nd] = (3.5-5.0) x 10(-2) mol/L; [styrene] = 5 mol/L; [Al]/[Nd] = 6-8 mol/mol; [H2O]/[Al] = 0.05-0.08 mol/mol; polymerization temperature around 70 degrees C. The percent yield of isotactic polystyrene (TY) is markedly affected by catalyst aging temperature. With increase of the aging temperature from 40 to 70 degrees C, TY increases from 9% to 48%. Using AlEt3 and Al(i-Bu)(2)H instead of Al(i-Bu)(3) decreases the yield of isotactic polystyrene. Different neodymium compounds give the following activity order: Nd(P-507)(3) > Nd(P-204)(3) > Nd(OPri)(3) > NdCl3 + C2HF5OH > Nd(naph)(3). With Nd(naph)(3) as catalyst, only atactic polystyrene is obtained. (C) 1998 John Wiley & Sons, Inc.

Isothermal and nonisothermal melt-crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II-->III transition, at a crystallization temperature of 239degrees, is found. The values of the nucleation parameter K-g for regimes II and III are estimated. The lateral-surface free energy, sigma = 3.24 erg cm(-2), the fold-surface free energy, sigma(e) = 52.3 +/- 4.2 erg cm(-2), and the average work of chain folding, q = 4.49 +/- 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be DeltaE = -830.7 kJ/mol and DeltaE = -315.9 kJ/mol, respectively.

Influence of intermolecular entanglements on the glass transition and structural relaxation behaviors of macromolecules. 2. Polystyrene and phenolphthalein poly(ether sulfone)

The effect of entanglements on the glass transition and structural relaxation behaviors has been studied for polystyrene (PS) and phenolphthalein poly(ether sulfone) (PES-C) samples by fast evaporation of the solution of concentrations varying from above the overlapping concentration to far below it, and compared to the results we have studied previously in PC. It has been found that for all the polymers we have studied, in the concentrated solution region, the T-g of the samples obtained from solution are independent of the change of concentration and are very close to that of normal bulk samples, whereas in the dilute solution region the T-g of the samples decrease with the logarithm of decreasing concentration. The critical concentrations that divide the two distinct regions for the three polymers are 0.9% g/mL for PC, 0.1% g/mL for PS, and 1% g/mL for PES-C. The decrease of T-g of the samples is interpreted by the decrease of intermolecular entanglements as the isolation of polymer chains, and the entanglement of polymer chains restrained the mobility of the segments. The structural relaxation behavior of the polymers is also found to be different from that of normal bulk samples. The enthalpies of single-chain samples are lower than that of the bulk ones, which correspond to the lower glass transition temperature; the peaks are lower and broader, and the relaxed enthalpy is much lower as compared to that of bulk samples. In the three polymers we have studied, the influence of change of entanglements on both the decrease in glass transition temperature and relaxed enthalpy is the most significant for PS and the least for PES-C. It is indicated that the interactions in the flexible polymers are weak; thus, the restraint of the entanglements on the mobility of the segments plays a more important role in the flexible polymers, and the change of entanglement in the flexible polymers has a more significant influence on the physical properties.

Rhythmic Growth-Induced Ring-Banded Spherulites with Radial Periodic Variation of Thicknesses Grown from Poly(epsilon-caprolactone) Solution with Constant Concentration

Birefringent ring-banded spherulites with radial periodic variation of thicknesses were grown from poly(epsilon-caprolactone) (PCL) solutions under conditions for which the Solution concentration was held constant during the whole development of the morphology. The as-grown ring-banded spherulites were investigated by optical (OM) and atomic force (AFM) microscopies, by transmission electron microscopy (TEM) of samples sectioned parallel to the plane of film, and also by electron diffraction (ED) and grazing incidence X-ray diffraction (GIXD) techniques.

Rhythmic growth of ring-banded spherulites in blends of liquid crystalline methoxy-poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring-banded spherulites in blends of liquid crystalline methoxy-poly(aryl ether ketone) (M-PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring-banded spherulites in the M-PAEK/PEEK blends is strongly dependent on the blend composition. In the M.-PAEK-rich blends, upon cooling, an unusual ring-banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M-PAEK/PEEK blend, ring-banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M-PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring-banded spherulite formation in the blends. In addition, the effects of M-PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed.

Formation of nonextinct ring-banded textures and multistacked lamella of tetra-aniline-block-poly(L-lactide) rod-coil diblock oligomer films induced by solvent vapor treatment

The self-assembly processes of the rod-coil diblock oligomer thin film of tetra-aniline (TANI)-block-poly(L-lactide) (PLLA) with different film thicknesses induced in the coil-selective solvent of acetone vapor at room temperature were studied. The morphologies of the oligomer films were determined by the film thickness. For the thicker film (232 nm), the nonextinct concentric ring-banded textures could form. While for the thinner and appropriate film (about 6 nm), multistacked diamond-shaped appearances with the periodic thickness being about 8.5 nm(6-nm-thick extended PLLA chain and 2.5-nm-thick p-pi conjugating TANI bimolecular layer) formed. The possible formation models of those two regular morphologies were presented in detail.

Influence of entanglements an the glass transition and structural relaxation behaviors of macromolecules. 1. Polycarbonate

We obtained the single-chain polycarbonate sample, by a new fast evaporation method and found that the polycarbonate sample obtained by this method is completely amorphous, while the polycarbonate sample obtained by other methods all have a certain degree of crystallinity. The glass transition temperature (T-g) of the sample decreases with the decreasing of concentration when the concentration of the prepared solution is below the critical value. The critical concentration we obtained from the T-g dependence of concentration is 0.9% g/mL and is in accord with that obtained by viscometry and light scattering methods directly from the solution. The structural relaxation behavior is found also different from that of a normal bulk sample of polycarbonate. The enthalpic peak of the single-chain sample is lower: than that of the bulk one, which corresponds to the lower glass transition temperature. The peak of the single-chain sample is lower and broader, and the relaxed enthalpy is much lower compared with that of the bulk sample. These results have been explained in terms of the effect of entanglement on the mobility of the segments in polymer and the compact conformation in the single-chain sample.

Stereospecific polymerization of styrene using a homogeneous lanthanide catalyst

Stereospecific polymerization of styrene was catalyzed by homogeneous neodymium phosphonate [Nd(P-507)(3)]-H2O-Al(i-Bu)(3) catalytic system. The polymer was separated into isotactic polystyrene and atactic polystyrene by extracting the latter with boiling 2-butanone. The conversion of styrene and the yield of isotactic polystyrene (IY) were influenced by the [H2O]/[Al(i-Bu)(3)] mole ratio and the solvent polarity. The reaction is first order with respect to monomer at 70 degrees C.

Morphology, tensile strength and thermal behavior of isotactic polypropylene/syndiotactic polystyrene blends compatibilized by SEBS copolymers

The effects of three triblock copolymers of poly [styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weight (MW) on the morphology, tensile strength and thermal behavior of isotactic polypropylene/syndiotactic polystyrene (iPP/sPS, 80/20) blend are investigated. Morphology observation shows that both the medium MW and the lower MW SEBS are more effective than the higher MW SEBS in compatibilizing the blends. Tensile tests revels both the medium and low MW compatibilizer lead to a significant improvement in tensile strength, while the higher MW compatibilizer is efficient in increasing the elongation at break of the blends. The localization of compatibilizers in the blends is observed by mean of SEM and the correlation between the distribution of the compatibilizers and mechanical properties of the blends is evaluated. The mechanical properties of the iPP/sPS blends depend on not only the interfacial activity of the compatibilizers but also the distribution of the compatibilizer in the blend. Addition of the compatibilizers to the blend causes a remarkable decrease in the magnitude of the crystallization peak of sPS at its usual T-c. Vicat softening points demonstrate that the heat resistance of iPP/sPS blend is much higher than that of the pure iPP.

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.

Kinetic and Size Control of Polystyrene and Polyacrylic Octadecyl Ester Lattices Via Polymerization in O/W Microemulsions

The kinetic studies of the acrylic octadecyl ester and styrene polymerization in microemulsion systems, (1) cetyl pyridine bromide (CPDB)/t-butanol/styrene/water; (2) CPDB/t-butanol/toluene + acrylic octadecyl ester (1:1, w/v)/ water; (3) cetyl pyridine bromide/styrene/formamide, were made by using dynamic laser light scattering techniques (DLS). The mechanisms of nucleation of latex particles were discussed. The most possible nucleation location of the styrene and acrylic octadecyl ester microlatex particles in aqueous microemulsion system is in aqueous phase via homogeneous nucleation. Meanwhile, parts of microlatex particles are possibly produced via swollen micelles (microemulsions) and monomer droplets nucleation. On the other hand, the most possible nucleation location of the styrene microlatex particles in nonaqueous microemulsion system is inside monomer droplets. The relationship between the amount of monomer and the size of microlatex was also investigated. It has been found that the size of microlatex particles could be controlled by changing the amount of monomer. (C) 2002 Elsevier Science B.V. All rights reserved.

Improving Nucleation in the Fabrication of High-Quality 3D Macro-Porous Copper Film through The Surface-Modification of A Polystyrene Colloid-Assembled Template

A new approach is developed to the fabrication of high-quality three-dimensional macro-porous copper films. A highly-ordered macroporous copper film is successfully produced on a polystyrene sphere (PS) template that has been modified by sodium dodecyl sulfate (SDS). It is shown that this procedure can change a hydrophobic surface of PS template into a hydrophilic surface. The present study is devoted to the influence of the electrolyte solution transport on the nucleation process. It is demonstrated that the permeability of the electrolyte solution in the nanochannels of the PS template plays an important role in the chemical electrodeposition of high-quality macroporous copper film. The permeability is drastically enhanced in our experiment through the surface modi. cation of the PS templates. The method could be used to homogeneously produce a large number of nucleations on a substrate, which is a key factor for the fabrication of the high-quality macroporous copper film.

Anisotropic Deformation Of Polystyrene Particles By Mev Au Ion Irradiation

MeV An irradiation leads to a shape change of polystyrene (PS) and SiO2 particles from spherical to ellipsoidal, with an aspect ratio that can be precisely controlled by the ion fluence. Sub-micrometer PS and SiO2 particles were deposited on copper substrates and irradiated with Au ions at 230 K, using an ion energy and fluence ranging from 2 to 10 MeV and 1 x 10(14) ions/cm(2) to 1 x 10(15) ions/cm(2). The mechanisms of anisotropic deformation of PS and SiO2 particles are different because of their distinct physical and chemical properties. At the start of irradiation, the volume of PS particles decrease, then the aspect ratio increases with fluence, whereas for SiO2 particles the volume remains constant. (C) 2008 Elsevier B.V. All rights reserved.