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.

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.

Preparation, characterization, and crystallization of naphthalene-labeled polypropylene

Naphthalene-labeled polypropylene (PP) was prepared by melt reaction of maleic anhydride-grafted-polypropylene (PP-g-MA) with 1-aminonaphthalene in a Barabender mixer chamber. The structure of the product was analyzed with fourier transform infrared (FT-IR), ultraviolet (UV) and fluorescence. The results showed that naphthyl groups grafted onto the PP molecular chains through the imide bonds formed between MA and 1-aminonaphthalene. The content of the chromophores was 1.8 X 10(-4) mol g(-1) measured by elemental analysis. Isothermal crystallization behavior was studied by differential scanning calorimeter (DSC). Labeled PP had a higher crystallization rate than PP-g-MA. Wide-angle X-Ray diffraction (WAXD) analysis revealed that labeled PP had higher crystallinity than PP-g-MA.

Crystal form transition during heating of solvent-induced crystalline syndiotactic polystyrene

The phase transition of two kinds of solvent-induced crystalline syndiotactic polystyrene (sPS). gamma-sPS and delta(c)-sPS, has been studied via WAXD and DSC. gamma-sPS transform to a-sPS at 195-225 degrees C before melt during heating, whereas delta(e)-sPS transform to first gamma-sPS and then a-sPS at 100-200 degrees C and 200-215 degrees C, respectively. The transition of delta(e)-gamma and gamma-a occurs for below melting point of sPS indicates they are all solid-solid transition.

Further study on double-melting endotherms of isotactic polypropylene

The origins of the single- and double-melting endotherms of isotactic polypropylene crystallized at different temperatures were studied carefully by differential scanning calorimetry, wide-angle X-ray diffraction, and small-angle X-ray scattering. The experimental data show that spontaneous crystallization occurs when the crystallization temperature is lower than 117 degrees C; thus the lamellae formed are imperfect. At a lower heating rate, the recrystallization or reorganization of these imperfect lamellae leads to double endotherms. On the other hand, when the crystallization temperature is higher than 136 degrees C, two major kinds of lamellae with different thickness are developed during the isothermal process, which also results in the double-melting endotherms. In the intermediate temperature range the lamellae formed are perfect, and there is only a single peak in the distribution of lamellar thickness. This explains the origin of the single-melting endotherm. (C) 2000 John Wiley & Sons, Inc.

A novel epitaxy of isotactic polypropylene (alpha phase) on PTFE and organic substrates

Isotactic polypropylene in its a modification (alpha iPP) crystallises epitaxially on polytetrafluoroethylene (PTFE) and several hemiacids or salts of substituted benzoic acids via a novel contact plane, namely (110): so far, the only known contact plane involved in alpha iPP homo- and hetero-epitaxies was (010). In spite of its complicated architecture (alternation of antichiral helices with different azimuthal settings), the (110)(alpha iPP) contact plane displays well defined, if not prominent, rows of methyl side chains parallel to the crystallographic (112) direction (at 57 degrees to the c-axis) and approximate to 5.5 Angstrom apart. The matching contact planes of the substrates display linear gratings made of rows of e.g. chlorine atoms or PTFE chains with similar approximate to 5.5 Angstrom inter-row or interchain distances. Various morphologies are observed in iPP thin films crystallised at different cooling rates in the presence of PTFE; they can be analysed in terms of a succession and interplay of successive epitaxies: initial alpha iPP/PTFE heteroepitaxy, followed by alpha iPP/alpha iPP and gamma iPP/alpha iPP homoepitaxies. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Functionalization of isotactic polypropylene with maleic anhydride by reactive extrusion: mechanism of melt grafting

In this work, chemical structures and molecular parameters of grafted materials of PP-g-MAH prepared by melt reactive extrusion were studied by using electrospray ionization-mass spectrometer and gel permeation chromatography. It was found that the initial radicals, due to homolitic scission of dicumyl peroxide could be combined with maleic anhydride (MAH) monomers as well as polypropylene (PP) molecular chains. The homopolymerization of MAH cannot occur and the MAH radicals undergo a dismutational reaction under the processing condition (180-190 degreesC). A modified mechanism of melt grafting MAH onto PP has been proposed tentatively on the basis of our experimental results and other experimental findings published in the literature. (C) 2001 Elsevier Science Ltd. All rights reserved.

Synthesis of a novel graft-like copolymer of syndiotactic polystyrene with polybutadiene

A novel graft-like copolymer of syndiotactic polystyrene (sPS) with polybutadiene (PB) was synthesized by polymerization of styrene in a toluene solution of PB using the cyclopentadiene titanium trichloride (CpTiCl3)/methylaluminoxane (MAO) catalytic system. The effect of PB on the crystallization behavior of the copolymer was investigated by differential scanning calorimetry and wide angle X-ray diffraction. Hydrogenation of the sPS/PB copolymer with p-toluenesulfonyl hydrazide afforded a PE-like copolymer.

Studies on the interfacial adhesion between functionalized polypropylene and polyamide 1010

The interface behavior of polyamide 1010 (PA1010) and polypropylene (PP) was studied. In order to improve their interfacial adhesion, functional PP was prepared by means of grafting glycidyl methacrylate (GMA) on PP main chains and used instead of plain PP. Several technological characterizations were performed here on their interfaces. ESCA was used to confirm that some kind of reaction occurred between end groups of PA1010 and epoxy species of PP-g-GMA. The peel test was adopted to measure interfacial adhesion. It was found that the fracture energy of interfaces between PA1010 and PP-g-GMA was dramatically increased with the content of GMA. Their interfaces were observed as being blurred by using SEM and TEM and a crack that could be seen in the case of the interfaces of the PA1010 and the plain PP disappeared.

Syndiotactic polystyrene/thermoplastic polyurethane blends using poly(styrene-b-4-vinylpyridine) diblock copolymer as a compatibilizer

The effect of adding diblock copolymer poly(styrene-b-4-vinylpyridine) (P(S-b-4VPy), to immiscible blends of syndiotactic polystyrene (sPS)/thermoplastic polyurethane (TPU) on the morphology, thermal transition, crystalline structure, and rheological and mechanical properties of the blends has been investigated. The diblock copolymer was synthesized by sequential anionic copolymerization and was melt-blended with sPS and TPU. Scanning electron microscopy (SEM) showed that the added block copolymer reduced the domain size of the dispersed phase in the blends. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) revealed that the extent of compatibility between sPS and TPU affected the crystallization of the sPS in the blends. Tensile strength and elongation at break increased, while the dynamic modulus and complex viscosity decreased with the amount of P(S-b-4VPy) in the blend. The compatibilizing effect of the diblock copolymer is the result of its location at the interface between the sPS and the TPU phases and penetration of the blocks into the: corresponding phases, i.e. the polystyrene block enters the noncrystalline regions of the sPS, and the poly(4-vinylpyridine) block interacts with TPU through intermolecular hydrogen bonding. (C) 1999 Elsevier Science Ltd. All rights reserved.

On morphology and the competition between crystallization and phase separation in polypropylene-polyethylene blends

Blends of polypropylene (PP) and low density polyethylene (LDPE) have been examined for a series of compositions using differential scanning calorimetry and permanganic etching followed by transmission electron microscopy. Thermal analysis of their melting and recrystallization behaviour suggests two possibilities, either that below 15 wt % PP the blends are fully miscible and that PP only crystallizes after LDPE because of compositional changes in the remaining melt, or else that the PP is separated, but in the form of droplets too small to crystallize at normal temperatures. Microscopic examination of the morphology shows that the latter is the case, but that a fraction of the PP is nevertheless dissolved in the LDPE. (C) 1998 Kluwer Academic Publishers.

Controlling factors for the occurrence of heteroepitaxy of polyethylene on highly oriented isotactic polypropylene

The controlling factors for the epitaxial crystallization of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) substrates have been studied in detail by means of transmission electron microscopy and electron diffraction. The results obtained in this work indicate that the crystallization process must be considered in the investigation of epitaxial growth of polymers on polymeric substrates, because of the unique morphological and crystallization characteristics of polymers. Crystallization rate has an important effect on the epitaxial crystallization of polymers. Higher rates result in the formation of thicker epitaxial layers. Isothermal crystallization temperature is another factor affecting epitaxial growth of polymers. Lower temperatures are favorable to epitaxial crystallization of polymers. There exists a critical epitaxial temperature at given experimental conditions, above which no epitaxial growth occurs at all. The influence of crystal dimensions of both the substrates and the deposited polymers on epitaxial growth confirms that secondary nucleation is an important controlling factor for the occurrence of epitaxial crystallization in polymers. The requirement satisfying the secondary nucleation criterion is that the substrate crystal dimension in the matching direction must be greater than the crystal thickness of the deposited polymer. Once the requirement of the secondary nucleation is satisfied, subsequent epitaxial growth is based on the lamellar growth habit of the deposited polymer itself. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Morphological studies of polyamide 1010/polypropylene blends

Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the morphology of blends of PA1010 and polypropylene (PP) compatibilized with polypropylene grafted with glycidyl methacrylate (PP-g-GMA). It is found that the morphologies are dependent on the content of glycidyl methacrylate in PP-g-GMA and the mixing time. The size of the dispersed PP particles decreases as the content of GMA in the PP-g-GMA increases for binary blends of PA1010 and PP-g-GMA. Similar results are obtained for changing the mixing time. Ternary blends of PA1010, PP, and PP-g-GMA indicate that morphologies depend on the content of glycidyl metyacrylate in the PP-g-GMA and the miscibility of PP and PP-g-GMA. By changing the content of GMA in PP-g-GMA, it was possible to introduce significant changes of morphology. A matrix removal TEM method is used to investigate the interfacial structure of PA1010/PP blends containing PP-g-GMA as a compatibilizer. This technique shows the reaction product between PA1010 and PP-g-GMA to be located at interface as a surrounding layer around domain particles. SEM observation on the interface shows that the adhesion between PA1010 and pure PP is very weak and their interface boundary is sharp. For the samples of PA1010 and PP-g-GMA, it was found that the interface was not so obvious, and the reaction between PA1010 and PP-g-GMA strengthens the interface significantly. (C) 1997 Elsevier Science Ltd.

Critical surface tension of acrylamide-grafted polypropylene copolymer by the contact angle method

The contact angles theta of polar liquids on PP-g-AM copolymer (AM content 0.19, 0.26, and 0.37 wt%) were measured. The critical surface tension gamma(c) of PP-g-AM films were evaluated by the Zisman plot (cos theta versus gamma(L)), the Young-Dupre-Good-Girifalco plot (1 + cos theta) versus 1/gamma(L)(0.5), and the log(1 + cos theta) versus log gamma(L) plot. The gamma(L) values estimated by the plot log(1 + cos theta) versus log gamma(L) were smaller than those obtained by the other plots.

Morphological, thermal, and mechanical properties of polypropylene/polycarbonate blend

This work deals with the effect of compatibilizer on the morphological, thermal, rheological, and mechanical properties of polypropylene/polycarbonate (PP/ PC) blends. The blends, containing between 0 to 30 vol % of polycarbonate and a compatibilizer, were prepared by means of a twin-screw extruder. The compatibilizer was produced by grafting glycidyl methacrylate (GMA) onto polypropylene in the molten state. Blend morphologies were controlled by adding PP-g-GMA as compatibilizer during melt processing, thus changing dispersion and interfacial adhesion of the polycarbonate phase. With PP-g-GMA, volume fractions increased from 2.5 to 20, and much finer dispersions of discrete polycarbonate phase with average domain sizes decreased from 35 to 3 mu m were obtained. The WAXD spectra showed that the crystal structure of neat PP was different from that in blends. The DSC results suggested that the degree of crystallization of PP in blends decreased as PC content and compatibilizer increased. The mechanical properties significantly changed after addition of PP-g-GMA. (C) 1997 John Wiley & Sons, Inc.