Microporous membranes obtained from polypropylene blends with superior permeability properties

A blend of two polypropylene resins, different in molecular structure, one with linear chains and the other with long chain branches, was investigated to develop microporous membranes through melt extrusion (cast film process) followed by film stretching. The branched component significantly affected the row‐nucleated lamellar crystalline structure in the precursor films. The arrangement and orientation of the crystalline and amorphous phases were examined by wide angle X‐ray diffraction and Fourier transform infrared spectroscopy methods. It was found that blending of a small amount of a long chain branched polypropylene improved the orientation of the both crystalline and amorphous phases in the precursor films. Annealing, followed by cold and hot stretching were consequently employed to generate and enlarge pores in the films as a result of lamellae separation. SEM micrographs of the surface of the membranes obtained from the blend revealed elongated thin fibrils and a large number of lamellae. The lamellae thickness for the blend was much shorter in comparison to that of the linear PP precursor film. The permeability of the samples to water vapor and N₂ was significantly enhanced (more than twice) for the blend system. The porosity of the blend membrane showed a significant improvement with a value of 53% compared to 41% for the linear PP membrane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 148–157, 2008     

Flow induced crystallization of long chain branched polypropylenes under weak shear flow

In the present work long chain branched polypropylene (LCB PP) polymers were prepared by linear polypropylene and multi-functional monomer through melt grafting reaction. A quantitative rheological method was adopted to analysis the structure parameters of LCB PP. The effects of chain branched level on the crystallization kinetics of PP were investigated by rheology, differential scanning calorimetry, polarized optical microscope and wide-angle X-ray diffraction. The dynamic viscoelastic properties of LCB PP showed that the increase in the chain branched level caused a typical deviation from the terminal behavior and a different distribution of the melt relaxation spectrum in the long relaxation time regime. It was found that the chain branched level had a significant effect on the flow induced crystallization (FIC) process of PP melts. The crystallization of LCB PP was more sensitive to shear flow than that of linear PP during induced period at low shear rates. This result also indicated that the longer relaxation time of the polymer chains played an important role in the nucleation of PP under shear flow fields. LCB PP with high chain branched level showed accelerated crystallization kinetics in comparison with that with low chain branched level.     

Foaming behavior of polypropylene/polystyrene blends enhanced by improved interfacial compatibility

A series of polypropylene (PP)/polystyrene (PS) blends were prepared by solvent blending with PS‐grafted PP copolymers (PP‐g‐PS) having different PS graft chain length as compatibilizers. The interfacial compatibility was significantly improved with increasing PS graft chain length until the interface was saturated at PS graft chain length being 3.29 × 10³ g/mol. The blends were foamed by using pressure‐quenching process and supercritical CO₂ as the blowing agent. The cell preferentially formed at compatibilized interface because of low energy barrier for nucleation. Combining with the increased interfacial area, the compatibilized interface lead to the foams with increased cell density compared to the uncompatibilized one. The increase in interfacial compatibility also decreased the escape of gas, held more gas for cell growth, and facilitated the increase in expansion ratio of PP/PS blend foams. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1641–1651, 2008     

The formation of γ‐crystal in long‐chain branched polypropylene under supercritical carbon dioxide

The crystallization behavior of long‐chain branched (LCB) polypropylene (PP) in the supercritical carbon dioxide (scCO₂) atmosphere was investigated to show the influences of LCB and CO₂ on the formation of γ‐crystal. The crystallization experiments were performed in CO₂ atmosphere with the pressure from 1.3 to 10.4 MPa and temperature between 90 and 130 °C. The effects of LCB level, CO₂ pressure, and crystallization temperature on the content of γ‐crystal were investigated. The results showed that the influence of LCB on the formation of γ‐crystal was obvious when PP was crystallized in CO₂. The content of γ‐crystal increased with LCB level and reached a maximum of 88.2%. It could be explained that, as LCB increased the chainfolding energy of PP molecular chain and hindered it from folding back into crystal lamella, which made the formation of γ‐crystal easier. However, CO₂ was the key factor in the formation of γ‐crystal, and the influence of CO₂ on γ‐crystal was much significant than that of LCB. It was believed that the increase of free volume after dissolving of CO₂ in PP was helpful in the formation of γ‐crystal. It was found that the content of γ‐crystal increased almost linearly with CO₂ pressure (CO₂ content), and the contribution of CO₂ to γ‐crystal increased with pressure, while that of LCB increased with temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 441–451, 2008     

Synthesis and properties of long‐chain branched poly(ether sulfone)s by self‐polycondensation of AB2 type macromonomers

Long‐chain branched poly(ether sulfone)s (PESs) were synthesized via self‐polycondensation of AB₂ macromonomers. The linear PES oligomers synthesized by self‐polycondensation of 4‐chloro‐4′‐(4‐hydroxyphenyloxy)diphenyl sulfone were terminated with 4‐(3,5‐methoxyphenoxy)‐4′‐fluorodiphenyl sulfone to form AB₂ macromonomer precursors. After conversion from methoxy to hydroxy groups, the AB₂ macromonomers were self‐polycondensed to form long‐chain branched PESs. NMR measurements support the formation of the target macromonomers ( = 2930–67,800 (g mol^?1); M_n = number average molecular weight) and long‐chain branched PESs. Gel permeation chromatography with multiangle light scattering measurements indicated the formation of high‐molecular‐weight (M_w) polymers over 10⁴. The root‐mean‐square radius of gyration (R_g) suggests that the shape of the long‐chain branched PES synthesized from small AB₂ macromonomers in solution is similar to that of hyperbranched polymers. Increasing resulted in larger R_g, suggesting a transition from hyperbranched to a linear‐like architecture in the resulting long‐chain branched PESs. Rheological measurements suggested the presence of strongly entangled chains in the long‐chain branched PES. Higher tensile modulus and smaller elongation at the break were observed in the tensile tests of the long‐chain branched PESs. It is assumed that the enhanced molecular entanglement points may act as physical crosslinks at room temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1825–1831     

Rheological properties of HyperMacs—long‐chain branched analogues of hyperbranched polymers

HyperMacs are long chain branched analogues of hyperbranched polymers, differing only in the sense that they have polymer chains, rather than monomers between branch points. Although the building blocks for HyperMacs and AB₂ macromonomers can be well defined in terms of molecular weight and polydispersity, the nature of the coupling strategy adopted for the synthesis of the HyperMacs results in branched polymers with a distribution of molecular weights and architectures. Melt rheology showed polystyrene HyperMacs to be thermorheologically simple, obeying William–Landel–Ferry behavior. Zero shear viscosities of the polymers were shown to increase with average molecular weight and the melts display shear‐thinning behavior. HyperMacs showed little evidence for relaxation by reptation and the rheological behavior agreed well with the Cayley tree model for hierarchical relaxation in tube models of branched polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2762–2769, 2007     

Synthesis of long‐chain‐branched polyethylene by ethylene homopolymerization with a novel nickel(II) α‐diimine catalyst

Long‐chain‐branched polyethylene with a broad or bimodal molecular weight distribution was synthesized by ethylene homopolymerization via a novel nickel(II) α‐diimine complex of 2,3‐bis(2‐phenylphenyl)butane diimine nickel dibromide ({[2‐C₆H₄(C₆H₅)]? N?C? (CH₃)C(CH₃)?N? [2‐C₆H₄(C₆H₅)]}NiBr₂) that possessed two stereoisomers in the presence of modified methylaluminoxane. The influences of the polymerization conditions, including the temperature and Al/Ni molar ratio, on the catalytic activity, molecular weight and molecular weight distribution, degree of branching, and branch length of polyethylene, were investigated. The resultant products were confirmed by gel permeation chromatography, gas chromatography/mass spectrometry, and ¹³C NMR characterization to be composed of higher molecular weight polyethylene with only isolated long‐branched chains (longer than six carbons) or with methyl pendant groups and oligomers of linear α‐olefins. The long‐chain‐branched polyethylene was formed mainly through the copolymerization of ethylene growing chains and macromonomers of α‐olefins. The presence of methyl pendant groups in the polyethylene main chain implied a 2,1‐insertion of the macromonomers into [Ni]? H active species. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1325–1330, 2005     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006     

Facile synthesis and characterization of hyperbranched poly(ether amide)s generated from Michael addition polymerization of in situ created AB2 monomers

A new straightforward strategy for synthesis of novel hyperbranched poly (ether amide)s from readily available monomers has been developed. By optimizing the reaction conditions, the AB₂‐type monomers were formed dominantly during the initial reaction stage. Without any purification, the AB₂ intermediate was subjected to further polymerization in the presence (or absence) of an initiator, to prepare the hyperbranched polymer‐bearing multihydroxyl end‐groups. The influence of monomer, initiator, and solvent on polymerization and the molecular weight (MW) of the resultant polymers was studied thoroughly. The MALDI–TOF MS of the polymers indicated that the polymerization proceeded in the proposed way. Analyses of ¹H NMR and ¹³C NMR spectra revealed the branched structures of the polymers obtained. These polymers exhibit high‐moderate MWs and broad MW distributions determined by gel permeation chromatography (GPC) in combination with triple detectors, including refractive index, light scattering, and viscosity detectors. In addition, the examination of the solution behavior of these polymers showed that the values of intrinsic viscosity [η] and the Mark–Houwink exponent α were remarkably lower compared with their linear analogs, because of their branched nature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4309–4321, 2007     

Gas solubility of carbon dioxide in poly(lactic acid) at high pressures: Thermal treatment effect

The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO₂ in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007     

Poly[1‐(trimethylgermyl)‐1‐propyne] and poly[1‐(trimethylsilyl)‐1‐propyne] with various geometries: Their synthesis and properties

The polymerization of 1,2‐disubstituted acetylenes [1‐(trimethylgermyl)‐1‐propyne and 1‐(trimethylsilyl)‐1‐propyne] initiated by Nb‐ and Ta‐based catalytic systems was studied within a wide temperature range (?10 to +80 °C) with solvents (cyclohexane, CCl₄, toluene, anisol, and n‐chlorobutane) with variable dielectric constants (2.023–7.390). Conditions ensuring the synthesis of poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP) containing 20–80% cis units and poly[1‐(trimethylgermyl)‐1‐propyne] (PTMGP) containing 3–65% cis units were determined. The PTMSP and PTMGP samples were amorphous, exhibited a two‐phase structure characterized by the presence of less ordered regions and regions with an enhanced level of ordering, and differed in solubility. A correlation was found between the cis/trans ratio and the morphology, the geometrical density of PTMSP and PTMGP films, and the gas permeability of the polymers. The gas permeability and solubility behavior of PTMSP and PTMGP were examined in terms of the molecular characteristics of the polymer samples (the thermodynamic Kuhn segment and the Kerr electrooptic effect). It was demonstrated that the gas permeability, as well as the solubility of the polymers, was defined by their supramolecular ordering, which depended on the lengths of continuous sequences composed of units of analogous microstructures and on the flexibility of macrochains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2133–2155, 2003     

Poly(caprolactone) containing highly branched segmented poly(ester urethane)s via A2 with oligomeric B3 polymerization

Highly branched, poly(caprolactone) (PCL) containing segmented poly(ester urethane)s were synthesized via polymerization of A₂ and oligomeric B₃ type monomers. An isocyanate functional butanediol‐based A₂ hard segment was synthesized and immediately reacted with a poly(caprolactone)‐based trifunctional (B₃) soft segment. Characterization of thermal properties using DMA and DSC analysis demonstrated that the PCL segment remained amorphous in branched poly(ester urethane)s. Conversely, the crystallinity of PCL segment was retained to some extent in a linear analogue with equivalent soft segment molecular weight. Tensile testing revealed a slight decrease in Young's modulus and tensile strength for the highly branched polymers compared with a linear analogue. However, highly branched poly(ester urethane)s demonstrated lower hysteresis. In addition to synthesis of highly branched polymers, poly(ester urethane) networks were synthesized from a highly branched hydroxyl‐terminated precursor and a low molar mass diisocyanate as the crosslinking agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6285–6295, 2008     

Tear anisotropy in films blown from polyethylenes of different macromolecular architectures

Blown films of different types of polyethylenes, such as branched low‐density polyethylene (LDPE) and linear high‐density polyethylene (HDPE), are well known to tear easily along particular directions: along the film bubble's transverse direction for LDPE and along the machine direction (MD) for HDPE. Depending on the resin characteristics and processing conditions, different structures can form within the film; it is therefore difficult to separate the effects of the crystal structure and orientation on the film tear behavior from the effects of the macromolecular architecture, such as the molecular weight distribution and long‐chain branching. Here we examine LDPE, HDPE, and linear low‐density polyethylene (LLDPE) blown films with similar crystal orientations, as verified by through‐film X‐ray scattering measurements. With these common orientations, LDPE and HDPE films still follow the usual preferred tear directions, whereas LLDPE tears isotropically despite an oriented crystal structure. These differences are attributed to the number densities of the tie molecules, especially along MD, which are considerably greater for linear‐architecture polymers with a substantial fraction of long chains, capable of significant extension in flow. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 413–420, 2005     

Synthesis and characterization of highly hindered and thermally stable poly(1,4‐spirobifluorenylenevinylene) derivative

A new poly(1,4‐spirobifluorenylenevinylene) having advantage PPV and spirobifluorene as new emissive family was synthesized. Compared with PPV derivatives that usually have a tolane bisbenzyl defect, the polymer has the defect free structure because of the steric hindrance of the asymmetric bulky spirobifluorenyl group. Compared with spirobifluorene derivatives that usually have a low solubility, the polymer has the good solubility in common organic solvents. The polymer was amorphous and showed high PL quantum efficiency and high thermal stability with high T_g. The PL emission peaks were shown at 480–490 nm in solution and film, respectively, which may represent the bluest emission peak reported for fully conjugated PPV derivatives. The study of thermal annealing of PL spectrum showed excimer formation inhibited. The thermal and optoelectronic properties of the polymer imply that it is a promising material for the PLED application. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 900–907, 2007.     

Influence of polypropylene topological structure evolution during melt branching reactive processing on its melt performances

Gel‐free long‐chain‐branched polypropylene (LCBPP) was prepared by the melt radical branching reaction in the presence of peroxide initiator 2,5‐dimethyl‐2,5‐di(tert‐butylperoxy) hexane peroxide, zinc dimethyldithiocarbamate, and trimethylolpropane triacrylate in a torque rheometer. It could be inferred that recombination between PP chains via radical coupled reaction took place and trimethylolpropane triacrylate was grafted onto PP backbone by the torque curves and Fourier transformed infrared spectroscopy results. The presence of long chain branches (LCB) for modified PP was verified by the gel permeation chromatography measurements and vGP plots. On the other hand, it was found that the topological structure of PP chains transformed from linear form to a long star‐like shape during the reaction progress, and the topological structure was directly determined by the radical reaction time. The topological structure of PP would further impact its melt behaviour. After complete melting of raw PP, “sparse and long” LCBPP firstly generated which possessed high melt strength owing to the increasing entanglement of long branching chains. And at the time corresponding to the summit of reaction peak on the torque curve, the modified LCBPP possess the highest melt strength owing to its long star topological structure. While as reaction time was prolonged, severe degradation of the LCBPPs would take place under too long mixing time and “dense and short” branches generated due to the residual radicals, with a sharp decline in melt strength.     

Extent of branching from linear viscoelasticity of long‐chain‐branched polymers

We present new results and examine literature data concerning the linear viscoelastic behavior of polyethylene with sparse to intermediate levels of long‐chain branching (LCB). These branched polymers displayed a common rheological signature, namely, a region of frequency‐independent loss tangent along with the corequisite scaling of the storage and loss moduli to the same frequency exponent. This apparent power‐law response occurred within a finite frequency window and bore resemblance to the behavior of physical gels. The appearance of this region, however, was the consequence of the presence of two distinct, yet partially overlapping, terminal relaxation processes. After considering the analogous relaxation behavior of wholly linear polymers with bimodal molecular weight distributions, we considered the polymers with LCB as blends of linear and branched species to develop a simple method of quantifying the extent of LCB. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1671–1684, 2004     

Melt rheology of polypropylene containing small amounts of high molecular weight chain. I. Shear flow

Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of high molecular weight polyethylene (PE) into PP. The viscoelastic properties of the high‐melt‐strength PP melts under shear flow were investigated. It was found that the rheological properties of the high‐melt‐strength PP were distinctly different from those of conventional PP. The elastic response at low frequencies was significantly enhanced in comparison with the conventional PP, implying a presence of a long relaxation time mode that was not revealed in conventional PP. In step‐shear measurements, the fast and slow relaxation processes that characterized the linear viscoelastic properties were observed also for nonlinear relaxation moduli. The dependence of the damping for the slow process of the high‐melt‐strength PP on shear strain was much weaker than that of the fast process. These rheological behaviors characterizing the long relaxation time mode were further enhanced with the increasing concentration of high molecular mass PE. The unusual shear rheological behaviors were discussed in view of the role of high molecular weight PE as a long relaxation time mode within PP. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2692–2704, 2001     

Synthesis of linear and hyperbranched poly(etherketone)s containing flexible oxyethylene spacers

As an alternative to strong acid reaction media for the Friedel–Crafts acylation for a polymer‐forming reaction, a mild polyphosphoric acid (PPA) with optimized amount of phosphorous pentoxide (P₂O₅) has been tested for the polymerization of AB monomers 4‐(2‐phenoxyethoxy)benzoic acid and 3‐(2‐phenoxyethoxy)benzoic acid, and an AB₂ monomer 3,5‐bis(2‐phenoxyethoxy)benzoic acid. The reaction progress of AB₂ monomer was conveniently traced by FTIR spectroscopy monitoring aromatic ketone (C?O) stretching bands arisen from carboxylic acid groups at the chain ends and carbonyl groups in the backbone as a function of reaction time at 110 °C. The resultant linear and hyperbranched polymers containing flexible oxyethylene spacers, which were prone to be hydrolyzed in strong acids at elevated temperature, displayed high intrinsic viscosities. Thus, the reaction medium PPA/P₂O₅ mixture as an electrophilic substitution reaction was indeed benign not to depolymerize growing polymer molecules but strong enough for the direct generation of carbonium ion from carboxylic acid to promote efficient polymerization. The resultant hyperbranched poly(etherketone) (PEK) displayed the best solubility among samples. All PEKs showed good thermal stability; glass transition temperatures were in the range of 90–117 °C; 5% weight loss generally occurred at greater than 345 °C in air. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5112–5122, 2007     

Miscibility and surface segregation in PVC/polyester blends—The influence of chain architecture and composition

Four poly(butylene adipate) (PBA) polyesters, the structure ranging from linear to highly branched, were synthesized and solution casted with poly(vinyl chloride) (PVC) in 20 or 40 wt % concentrations to evaluate the influence of polyester chain architecture on miscibility, surface segregation, and mechanical properties. The miscibility of PVC and polyesters is based on specific interactions between the carbonyl group in the polyester and PVC. These interactions cause a shift in the carbonyl absorption band in the FTIR spectra. The shifting of the carbonyl absorption band was more significant for all the 40 wt % blends compared with the blends containing 20 wt % of the same polyester. In the 20 wt % blends surface segregation and enrichment of polyester at the blend surface increased as a function of branching. However, all the films containing 40 wt % of polyester had similar surface composition. This is explained by better miscibility and stronger intermolecular interactions in the 40 wt % blends, which counteract the effect of branching on the surface segregation. High degree of branching resulted in poor miscibility with PVC and poor mechanical properties. A linear or slightly branched polyester structure, however, resulted in good miscibility and desirable blend properties. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1552–1563, 2007