Enhanced crystallization of the gamma-form of propylene-ethylene copolymer in its miscible blends with propylene homopolymer

BACKGROUND: How to promote the formation of the gamma-form in a certain propylene-ethylene copolymer (PPR) under atmospheric conditions is significant for theoretical considerations and practical applications. Taking the epitaxial relationship between the alpha-form and gamma-form into account, it is expected that incorporation of some extrinsic alpha-crystals, developed by propylene homopolymer (PPH), can enhance the crystallization of the gamma-form of the PPR component in PPR/PPH blends.RESULTS: The PPH component in the blends first crystallizes from the melt, and its melting point and crystal growth rate decrease with increasing PPR fraction. On the other hand, first-formed alpha-crystals of the PPH component can induce the lateral growth of PPR chains on themselves, indicated by sheaf-like crystal morphology and positive birefringence, which is in turn responsible for enhanced crystallization of the gamma-form of the PPR component.

Shape-memory and biocompatibility properties of segmented polyurethanes based on poly(L-lactide)

A series of segmented poly (L-lactide)-polyurethanes (PLA-PU) were synthesized by a two-step method, with oligo-poly(L-lactide) (PLA) as the soft segments and the reaction product of 2,4-toluene diisocyanate(TDI) and ethylene glycol(EG) as the hard segments. The shape memory properties of PLA-PUs were examined. The processed PLA-PUs could recover almost 100% to their original shape within 10 degrees C from the lowest recovery temperature. In the recovery process, the PLA-PUs showed a maximum contracting stress of shape change in the range of 1.5-4 MPa depending on the PLA segmental length and the hard-segmental content and higher than that of poly (e-caprolactone polyurethane) (PCL-PU). Besides, the influence of deforming and fixing temperatures on shape memory properties of PLA-PU was studied in detail. They could affect not only the recovery temperature but also the maximum contracting stress. The experiments of cell incubation were used to evaluate the biocompatibility of PLA-PU. The results show that the biocompatibility of PLA-PU is comparable to that of the pure PLA. This kind of polyurethane can be used as implanted medical devices with a shape memory property.

Effect of swelling response of the support particles on ethylene polymerization

Macroporous and modified macroporous poly(styrene-co-methyl methacrylate-co-divinylbenzene) particles (m-PS and mm-PS) supported Cp2ZrCl2 were prepared and applied to ethylene polymerization using methylaluminoxane (MAO) as cocatalyst. The influences of the swelling response of the support particles on the catalyst loading capabilities of the supports as well as on the activities of the supported catalysts were studied. It was shown that the Zr loadings of the supports and the activities of the supported catalysts increased with the swelling extent of the support particles. The m-PS or mm-PS supported catalysts exhibited very high activities when the support particles were well swollen, whereas those catalysts devoid of swelling treatment gave much lower activities. Investigation on the distribution of the supports in the polyethylene by TEM indicated that the swelling of the support particles allowed the fragmentation of the catalyst particles. In contrast, the fragmentation of the support particles with poor swelling was hindered during ethylene polymerization.

The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.

Preparation of macroporous functionalized polymer beads by a multistep polymerization and their application in zirconocene catalysts for ethylene polymerization

Macroporous functionalized. polymer beads of poly(4-vinylpyridine-co-1,4-divinylbenzene) [P(VPy-co-DVB)] were prepared by a multistep polymerization, including a polystyrene (PS) shape template by emulsifier-free emulsion polymerization, linear PS seeds by staged template suspension polymerization, and macroporous functionalized polymer beads of P(VPy-co-DVB) by multistep seeded polymerization. The polymer beads, having a cellular texture, were made of many small, spherical particles. The bead size was 10-50 mum, and the pore size was 0.1-1.5 mum. The polymer beads were used as supports for zirconocene catalysts in ethylene polymerization. They were very different from traditional polymer supports. The polymer beads could be exfoliated to yield many spherical particles dispersed in the resulting polyethylene particles during ethylene polymerization. The influence of the polymer beads on the catalytic behavior of the supported catalyst and morphology of the resulting polyethylene was investigated.

Preparation of poly(4-vinylpyridine)/silica hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

Poly(4 - vinylpyridine)/silica( PVP/SiO2) organic - inorganic nanoscale hybrid was prepared using sol - gel method, in which PVP was used as an organic component and TEOS as a SiO2 precusor, This hybrid was used as CpTiCl3 support. The XPS and IR measurements showed that two kinds of catalytic active site were formed through analyzing the interaction mode between support and CpTiCl3. The results of styrene polymerization showed that syndiotactic was the highest at 50 degreesC. The catalytic activity was 1.09 x 10(6) g PS/ (mol Ti . h) at 70 degreesC when n(Al)/n(Ti) = 1500. GPC results showed a bimodal molecular weight distribution.

Mechanism-transformation synthesis and characterization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer

By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.

Polymer-supported zirconocene catalyst for ethylene polymerization

The use of crosslinked poly(styrene-co-4-vinylpyridine) having functional groups as the support for zirconocene catalysts in ethylene polymerization was studied. Several factors affecting the activity of the catalysts were examined. Conditions like time, temperature, Al/N (molar ratio), Al/Zr (molar ratio), and the mode of feeding were found having no significant influence on the activity of the catalysts, while the state of the supports had a great effect on the catalytic behavior. The activity of the catalysts sharply increased with either the degree of crosslinking or the content of 4-vinylpyridine in the support. Via aluminum compounds, AlR3 or methylaluminoxane (MAO), zirconocene was attached on the surface of the support. IR spectra showed an intensified and shifted absorption bands of C-N in the pyridine ring, and a new absorption band appeared at about 730 cm(-1) indicating a stable bond Al-N formed in the polymer-supported catalysts. The formation of cationic active centers was hypothesized and the performance of the polymer-supported zirconocene was discussed as well. (C) 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 37-46, 1999.

Liquid crystalline polymer as a processing agent in blends of poly(ether-ketone)/LCP70

Blends of a liquid crystalline thermotropic copolyester (LCP70) and an amorphous phenolphthalein based poly(ether-ketone)(PEK-C) with two viscosities were prepared by melt blending. The blends' morphology, rheological and mechanical properties were investigated by DSC, SEM, mechanical and rheological tests. It was observed that the optimum composition of the PEK-C/LCP70 blend was 10 wt% LCP for both mechanical and rheological properties. When the LCP content was less than 10%, the LCP phase existed as finely dispersed fibrous domains with a diameter of about 1 mu m in the matrix, and both tensile and flexural properties were improved. In contrast, when the LCP content reached 20% or more, the LCP domains coalesced to ellipsoidal particles with a diameter of about 5 mu m, and the mechanical properties decreased as a result. It is demonstrated that pure PEK-C with a high viscosity which was difficult to process by melt extrusion, could be extruded conveniently when 10% LCP70 was incorporated. It is emphasized that LCP not only can be used as a reinforcing phase but also an effective processing agent for engineering thermoplastics, especially for those with high viscosity and narrow processing window. (C) 1997 Elsevier Science Ltd.

Rheological properties and crystallization behavior of yttrium oxide filled low ethylene content polypropylene copolymer

The rheological properties and crystallization characteristics of low ethylene content poly propylene (EPM) with and without Yittrium oxide (Y2O3) as a filler was investigated by cone-plate viscometer and differential scanning calorimetry. Yittrium oxide had a profound effect on the viscosities of the systems. To determine the nonisothermal crystallization rate of the materials, a new estimation method was used. From the results, we can conclude that Y2O3 acts as a nucleating agent, which increased the crystallization rate of the EPM. (C) 1996 John Wiley & Sons, Inc.

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).

MISCIBILITY OF POLY(EPICHLOROHYDRIN) WITH POLY(VINYL ACETATE) AND POLY(STYRENE-CO-ACRYLONITRILE)

The phase behaviours of poly(vinyl acetate) (PVAc) and poly(styrene-co-acrylonitrile)s (SAN) with poly(epichlorohydrin) (PECH) were examined using differential scanning calorimetry and an optical method using a hot plate. The PECH/PVAc blends showed LCST behaviour. The observed miscibility is thought to be a result of hydrogen-bonding interactions between the alpha-hydrogen atoms of PECH and the carbonyl groups of PVAc. Two SAN copolymers with an acrylonitrile (AN) content of 18 wt% (SAN18) and 25 wt% (SAN25), respectively, were also found to exhibit miscibility with PECH. No phase separation occurred by heating up to about 280-degrees-C, and the individual blend has a single, composition-dependent glass transition temperature. The formation of miscible PECH/SAN blends can be considered as a result of the intramolecular repulsion between styrene and AN units in SAN.

Degradation of poly-L-lactide. Part2 : increased temperature accelerated degradation

Poly-L-lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioresorbable. The degradation of PLLA proceeds through hydrolysis of the ester linkages in the polymer's backbone; however, the time for the complete resorption of orthopaedic devices manufactured from PLLA is known to be in excess of five years in a normal physiological environment. To evaluate the degradation of PLLA in an accelerated time period, PLLA pellets were processed by compression moulding into tensile test specimens, prior to being sterilized by ethylene oxide gas (EtO) and degraded in a phosphate-buffered solution (PBS) at both 50°C and 70°C. On retrieval, at predetermined time intervals, procedures were used to evaluate the material's molecular weight, crystallinity, mechanical strength, and thermal properties. The results from this study suggest that at both 50°C and 70°C, degradation proceeds by a very similar mechanism to that observed at 37°C in vitro and in vivo. The degradation models developed also confirmed the dependence of mass loss, melting temperature, and glass transition temperature (Tg) on the polymer's molecular weight throughout degradation. Although increased temperature appears to be a suitable method for accelerating the degradation of PLLA, relative to its physiological degradation rate, concerns still remain over the validity of testing above the polymer's Tg and the significance of autocatalysis at increased temperatures.

Processing, Annealing and Sterilisation of Poly-L-Lactide.

Poly--lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioabsorbable. Degradation of PLLA proceeds through hydrolysis of the ester bonds in the polymer chains and is influenced significantly by the polymer's molecular weight and crystallinity. To evaluate the effects of processing and sterilisation on these properties, PLLA pellets were either compression moulded or extruded, subjected to annealing at 120°C for 4 h and sterilised by ethylene oxide (EtO) gas. Procedures were used to evaluate the mechanical properties, molecular weight and crystallinity. Upon processing, the crystallinity of the material fell from 61% for the PLLA pellets to 12% and 20% for the compressed and extruded components, respectively. After annealing, crystallinity increased to 43% for the compression-moulded material and 40% for the extruded material. Crystallinity further increased upon EtO sterilisation. A slight decrease in molecular weight was observed for the extruded material through processing, annealing and sterilisation. Young's modulus generally increased with increasing crystallinity, and extension at break and tensile strength decreased. The results from this investigation suggest that PLLA is sensitive to processing and sterilisation, altering properties critical to its degradation rate.

Non-ideal behaviour of a room temperature ionic liquid in an alkoxyethanol or poly ethers at T = (298.15 to 318.15) K

Non-ideal behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] in ethylene glycol monomethyl ether; CH3OCH2CH2OH (EGMME), ethylene glycol dimethyl ether; CH3OCH2CH2OCH3 (EGDME) and diethylene glycol dimethyl ether; CH3(OCH2CH2)2OCH3 (DEGDME) have been investigated over the whole composition range at T = (298.15 to 318.15) K. To gain insight into the mixing behaviour, results of density measurements were used to estimate excess molar volumes, image, apparent molar volumes, Vphi,i, partial molar volumes, image, excess partial molar volumes, image, and their limiting values at infinite dilution, image, image, and image, respectively. Volumetric results have been analyzed in the light of Prigogine–Flory–Patterson (PFP) statistical mechanical theory. Measurements of refractive indices n were also performed for all the binary mixtures over whole composition range at T = 298.15 K. Deviations in refractive indices ?phin and the deviation of molar refraction ?xR have been calculated from experimental data. Refractive indices results have been correlated with volumetric results and have been interpreted in terms of molecular interactions. Excess properties are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors.