Synthesis and thermal transitional properties of side-chain liquid crystalline polyacrylates containing para-nitroazobenzene as mesogenic groups

The synthesis and characterization of side-chain liquid crystalline (LC) polyacrylates containing para-nitroazobenzene (Pn) as mesogenic groups were described. Homopolymers with 3 and 4 carbon atoms in the spacers were non-LC polymers; for homopolymers with 6 carbon atoms in the spacer, nematic LC behavior was observed. Copolymers with acrylic acid as one component exhibited an S-Ad phase according to the WAXD results which showed the d/l of 1.4-1.54 for the copolymers with 3, 4, and 6 carbon atoms in the spacers. Considering the molecular structure as well as the WAXD results of the copolymers, the possible molecular arrangement in the smectic Sad phase was proposed, in which the smectic layers were composed of the antiparallel mesogens and the antiparallel arrangement was considered to be enhanced due to the H bond between - COOH and - NO2. The stress-induced orientational phenomena of Pn in the LC states was also discussed. (C) 1996 John Wiley & Sons, Inc.

Phase behavior in mixtures of a homopolymer and a block copolymer .4. SALS and SAXS studies

Phase behavior of blends of poly(vinyl methyl ether) (PVME) with four styrene-butadienestyrene (SBS) triblock copolymers, being of various molecular weights, architecture, and compositions, was investigated by small-angle light scattering. Small-angle X-ray scattering investigation was accomplished for one blend. Low critical solution temperature (LCST) and a unique phase behavior, resembling upper critical solution temperature (UCST), were observed. It was found that the architecture of the copolymer greatly influenced the phase behavior of the blends. Random phase approximation theory was used to calculate the spinodal phase transition curves of the ABA/C and BAB/C systems; LCST and resembling UCST phase behavior were observed as the parameters of the system changed. Qualitatively, the experimental and the theoretical results are consistent with each other. (C) 1996 John Wiley & Sons, Inc.

Copolymerization of styrene with butadiene and isoprene using a rare earth catalyst

In the copolymerization of styrene-butadiene and styrene-isoprene, a novel rare earth catalyst system (CF3CO2)(3)Ln/R(3-n)AlH(n)/(CH3)(3)CCH2Br (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; R = Me-, Et-, i-Bu-, and Oct-; n = 0 and 1) has been studied. The 1, 4 unit contents in the copolymers obtained are found to range from 64.4 to 99.6% with St contents of 5.2 to 59.9%, and intrinsic viscosities of 0.1 to 0.5 dl g(-1) measured by i.r., H-1 n.m.r. and C-13 n.m.r. spectra. From the calculated data of linked ratios, a change in the microstructure is induced by the styrene unit, probably adjacent to the butadiene or isoprene unit. An interesting result is that the ratios of styrene unit linked with 1, 2 or 3,4 units in the copolymers are far higher than in copolymers obtained with the nickel catalyst. The experimental results are discussed in terms of rare earth pi-allyl coordination and back-biting mechanism.

Poly(epsilon-caprolactone)/poly(ethylene oxide) diblock copolymer .1. Isothermal crystallization and melting behavior

The isothermal crystallization and melting behavior of the poly(epsilon-caprolactone) (PCL)/poly(ethylene oxide)(PEO) diblock copolymer has been studied by WAXD, SAXS, and DSC methods. Only the PCL block is crystallizable; the PEO block of weight fraction 20% cannot crystallize, although its corresponding homopolymer has strong crystallizability. The long period, amorphous layer, and crystalline lamella of the PCL/PEO block copolymer all increase with the rise in the crystallization temperature, and the thickness of the amorphous layer is much larger than that of crystalline lamella due to the existence of the PEO block in the amorphous region. The isothermal crystallization of the PCL/PEO block copolymer is investigated by using the theory of Turnbull and Fischer. It is found that the amorphous PEO block has a great influence on the nucleation of PCL block crystallization, and the extent of this influence depends on crystallization conditions, especially temperature. The outstanding characteristics are the phenomenon of the double melting peaks in the melting process of the PCL/PEO block copolymer after isothermal crystallization at different temperatures and the transformation of melting peaks from double peaks to a single peak with variations in the crystallization condition. They are related mainly to the existence of the PEO block bonding chemically with the PCL block. In summing up results of investigations into the crystallization and melting behavior of the PCL/PEO block copolymer, it is interesting to notice that when the PCL/PEO block copolymer crystallizes at three different crystallization temperatures, i.e., below 0 degrees C, between 0 and 35 degrees C, and above 35 degrees C, the variation of peak melting temperature is similar to that of overall crystallization rates in the process of isothermal crystallization. The results can be elucidated by the effect of the PEO block on the crystallization of the PCL block, especially its nucleation. (C) 1996 John Wiley & Sons, Inc.

MODIFICATION OF PP/HDPE BLENDS BY PP-PE SEQUENTIAL POLYMERIZATION PRODUCT

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends depends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. (C) 1995 John Wiley & Sons, Inc.

EFFECT OF ETHYLENE-PROPYLENE COPOLYMER WITH RESIDUAL PE CRYSTALLINITY ON MECHANICAL-PROPERTIES AND MORPHOLOGY OF PP/HDPE BLENDS

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispersed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. (C) 1995 John Wiley & Sons, Inc.

PLASMA-INDUCED GRAFTING OF STYRENE ONTO NASCENT POLYETHYLENE POWDER

In this paper, the graft copolymers of styrene to nascent linear polyethylene reactor powders were prepared through plasma graft polymerization. The grafting reaction was initiated by the alkyl radicals formed on the surface of nascent polyethylene with plasma treatment as indicated by electron spin resonance spectra. In graft copolymerization by alkyl radicals, the grafting yield increased with either the plasma power or the plasma treatment lime. Compared with ordinary polyethylene powders, nascent polyethylene reactor powders were found to be more easily plasma-grafted. This has been attributed to the greater sensitivity to irradiation in producing reactive centres under the same conditions. High density polyethylene showed almost the same grafting yield as linear low density polyethylene at 50 degrees C. The surface morphology of nascent polyethylene observed by scanning electron microscope before and after the grafting showed that the silk-like fibrils were not destroyed by plasma treatment.

SYNTHESIS OF A POLYETHYLENE-GRAFT-POLYSTYRENE COPOLYMER AND ITS COMPATIBILIZATION FOR LINEAR LOW-DENSITY POLYETHYLENE/POLY(PHENYLENE OXIDE) BLENDS

Based on unsteady diffusion kinetics, polyethylene(PE)-graft-polystyrene (PS) copolymers were designed and synthesized with a heterogeneous high yield titanium-based catalyst by copolymerization of ethylene with a PS-macromonomer using 1-hexene as a short chain agent to promote the incorporation of the PS-macromonomer. The presence of 1-hexene facilitated the diffusion of the PS-macromonomer, giving rise to the significantly increased incorporation of the PS-macromonomer. Compatibilization of blends of linear low density polyethylene (LLDPE)/poly(phenylene oxide) (PPO) with the PE-g-PS copolymer were investigated using scanning electron microscopy (SEM) and dynamic mechanical analysis (DMA).

ULTRASTRUCTURE OF LIQUID-CRYSTALLINE POLYACRYLATES CONTAINING P-NITRO AZOBENZENE

The phase behaviour ai the side chain liquid crystalline polyacrylates containing p-nitro azobenzene was studied bg DSC, WAXD and the polarized optical microscopy. It was shown that nematic phase can be formed for homopolymer HP6, no LC phase can be observed for HF3 and HP4; whereas smectic S-Ad phase can be obtained tor P-n when n was equal to 3,4, 6,8. The unique phase behaviour of the copolymers P-n was due to the existence of H bond between -COOH and -NO2 which lias been confirmed by FTIR. The molecular arrangement of the copolymers in their LC states was proposed from the results of WAXD and FTIR.

SYNTHESIS AND PROPERTIES OF POLY(ANILINE-CO-ANISIDINE)

Aniline and ortho-anisidine were chemically copolymerized at various temperatures and monomer compositions. Copolymers completely soluble in THF are prepared and characterized.

PHASE-BEHAVIOR IN MIXTURES OF A HOMOPOLYMER AND A BLOCK-COPOLYMER .1. FTIR AND DSC STUDIES

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm-1 region due to COCH3 band of PVME and peak position of 698 cm-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. (C) 1995 John Wiley & Sons, Inc.

SYNTHESIS AND CHARACTERIZATION OF POTENTIALLY BIODEGRADABLE THERMOTROPIC POLYESTERS BASED ON P-HYDROXYBENZOIC ACID AND GLYCOLIC ACID

The synthesis of novel thermotropic liquid crystalline copolyesters derived from aliphatic hydroxy acid (glycolic acid, GA) and aromatic hydroxy acid (p-hydroxybenzoic acid, PHBA) via a melt-copolycondensation process in the presence of various catalysts

SPREADING AND TRANSFER BEHAVIOR OF POLY(2-ACRYLAMIDOHEXADECYLSULFONIC ACID-CO-STYRENE) MONOLAYERS

The spreading behavior of poly(2-acrylamidohexadecylsulfonic acid-co-styrene) (PAMC16SSt) random co-polymers with various compositions was investigated by measurements of the surface pressure-area (pi-A) isotherms. The random copolymers formed stable cond

INTERFACIAL BEHAVIOR OF COMPATIBILIZERS IN POLYMER BLENDS

From an analysis of the literature and our experimental results, we have established that interfacial tension is a function of the concentration of a compatibilizer, and put forward a 'three-stage' physical model to account for the compatibilizing behavio