Influence of long‐chain branching on the miscibility of poly(ethylene‐r‐ethylethylene) blends with different microstructures

The melt miscibility of two series of poly(ethylene‐r‐ethylethylene) (PE_Exx) polymers with different percentages (xx) of ethylethylene (EE) repeat units was examined with small‐angle neutron scattering (SANS). The first series consisted of comb/linear blends in which the first component is a heavily branched comb polymer (B90) containing 90% EE and an average of 62 long branches with a weight‐average molecular weight (M_W) of 5.5 kg/mol attached to a backbone with M_W = 10.0 kg/mol. The comb polymer was blended with six linear PE_Exx copolymers, all of which had M_W ≈ 60 kg/mol and EE percentages ranging from 55 to 90%; they were denoted L55 to L90, with the number referring to the percentage of EE repeat units. The second series consisted of linear/linear blends; the first component, with M_W = 220 kg/mol and 90% EE, was denoted L90A, and the second components were the same series of linear polymers, with M_W ≈ 60 kg/mol and various EE compositions. The concentrations investigated were 50/50 w/w, except for the blend of branched B90 and linear L90 (both components were 90% EE), for which 25/75 and 75/25 concentrations were also examined. The SANS results indicated that for the comb/linear blends, only the dB90/L90 blends were miscible, whereas the other five blends phase‐separated; for the linear/linear blends, dL90A/L83 and dL90A/L78 were miscible, whereas the other three blends were immiscible. These results indicate that long‐chain branching significantly narrowed the miscibility window of these polyolefin blends. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 466–477, 2002; DOI 10.1002/polb.10102     

Effect of chain blockiness on the phase behavior of ethylene‐octene copolymer blends

New challenges and opportunities for polyolefin blends arise from the recent introduction of olefin block copolymers (OBCs). In this study, the effect of chain blockiness on the miscibility and phase behavior of ethylene‐octene (EO) copolymer blends was studied. Binary blends of two statistical copolymers (EO/EO blends) that differed in comonomer content were compared with blends of an EO with a blocky EO copolymer (EO/OBC blends). The blends were rapidly quenched to retain the phase morphology in the melt and the phase volumes were obtained by atomic force microscopy (AFM). Two EOs of molecular weight about 100 kg/mol were miscible if the difference in octene content was less than about 10 mol % and immiscible if the octene content difference was greater than about 13 mol %. The blocky nature of the OBCs reduced the miscibility and broadened the partial miscibility window of the EO/OBC blends compared with the EO/EO blends. The EO/OBC blends were miscible if the octene content difference was less than 7 mol % and immiscible above 13 mol % octene content difference. It was also found that the phase behavior of EO/OBC blends strongly depended on blend composition even for constituent polymers of about the same molecular weight. Significantly more demixing was observed in an OBC‐rich blend (EO/OBC 30/70 v/v) than in an OBC‐poor blend (EO/OBC 70/30 v/v). An interpretation based on extractable fractions of the OBC described the major features of the EO/OBC (30/70 v/v) blends. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1554–1572, 2009     

Partially miscible EVOH/copolyamide‐6/6.9 blends: The effect of stretching on the structure

Binary blends of random copolymers, ethylene‐vinyl‐alcohol (EVOH) consisting of 38 mol % ethylene and Copolyamide‐6/6.9 with an approximate 1 : 1 comonomer ratio, were prepared via blown‐film extrusion and uniaxial stretching. The anisotropy induced by the uniaxial deformation of the polymer blends was characterized by X‐ray diffraction and birefringence measurements. The stretched films also were investigated via oxygen permeability. The results showed a sharp decrease in the apparent crystallite size throughout the entire composition range in comparison to the blown films. However, the order perceived within the amorphous phase in the EVOH‐rich blends increased (decrease in oxygen permeability), whereas in the copolyamide‐rich blends, orientation resulted in a decrease in the amorphous phase order (increase in permeability). Apparently, orientation destroyed the amorphous interpolymer complex. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 813–822, 2000     

Interfacial living radical copolymerization of oil‐ and water‐soluble comonomers to form composite polymer capsules

The suspension copolymerization of methyl methacrylate with hydroxy‐functional poly(ethylene glycol) monomethacrylate (PEGMA) by atom transfer radical polymerization (ATRP) yielded soluble, controlled‐molecular‐weight amphiphilic copolymers (weight‐average molecular weight/number‐average molecular weight <1.3). Despite extensive partitioning of PEGMA into the water phase, copolymers containing up to 24 mol % PEGMA were formed in the oil phase, from comonomer feeds containing 30 mol % PEGMA. Conversions by suspension polymerization were comparable to those obtained by solution polymerization, at over 70%. Suspension copolymers with high PEGMA contents contained high‐molecular‐weight polymer formed by uncontrolled polymerization, unless poly(vinyl pyrrolidone) was added to displace the growing polymer from the interface. The addition of diethylene glycol dimethacrylate gave capsules at 17 mol % PEGMA with ATRP, whereas conventional free‐radical polymerization required 24 mol % PEGMA to form capsules. The lower PEGMA level required for capsule formation with ATRP was attributed to the lower rates of propagation and crosslinking and to improved incorporation of PEGMA into the final gels. Suspension ATRP with 24 mol % PEGMA in the feed gave two‐layer capsule walls consisting of an inner layer visible by transmission electron microscopy and an outer layer visible by both transmission electron microscopy and environmental scanning electron microscopy, which indicated a compositional gradient across the capsule wall. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 156–171, 2006     

A study of the blending of ethylene–styrene copolymers differing in the copolymer styrene content: Miscibility considerations

Blends of two or more ethylene–styrene (ES) copolymers that differed primarily in the comonomer composition of the copolymers were studied. Available thermodynamic models for copolymer–copolymer blends were utilized to determine the criteria for miscibility between two ES copolymers differing in styrene content and also between ES copolymers and the respective homopolymers, polystyrene and linear polyethylene. Model estimations were compared with experimental observations based primarily on melt‐blended ES/ES systems, particularly via the analysis of the glass‐transition (T_g ) behavior from differential scanning calorimetry (DSC) and solid‐state dynamic mechanical spectroscopy. The critical comonomer difference in the styrene content at which phase separation occurred was estimated to be about 10 wt % for ES copolymers with a molecular weight of about 10⁵ and was in general agreement with the experimental observations. The range of ES copolymers that could be produced by the variation of the comonomer content allowed the study of blends with amorphous and semicrystalline components. Crystallinity differences for the blends, as determined by DSC, appeared to be related to the overlapping of the T_g of the amorphous component with the melting range of the semicrystalline component and/or the reduction in the mobility of the amorphous phase due to the presence of the higher T_g of the amorphous blend component. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2976–2987, 2000     

Poly(ethylene terephthalate) copolymers containing nitroterephthalic units. I. Synthesis and characterization

The synthesis, microstructure, and thermal behavior of a series of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units are described. These novel copolyesters were synthesized by transesterification followed by melt copolycondensation of dimethyl terephthalate and dimethyl nitroterephthalate mixtures with ethylene glycol. The molar ratio of the two comonomers in the feed varied from 95/5 to 25/75. Furthermore, PET and poly(ethylene nitroterephthalate) homopolymers were synthesized with the same method and comparatively studied. Copolyester compositions were practically the same as in the feed, and weight‐average molecular weights ranged from 10,000 to 60,000. The two monomeric units were randomly distributed along the polymer chain, and the experimentally determined average sequence lengths were in accordance with ideal copolycondensation statistics. Melting temperatures and enthalpies of the copolyesters decreased with increasing content in nitroterephthalic units, and they all showed a single glass‐transition temperature superior to that of PET. They appeared to be stable up to 300 °C, and thermal degradation occurred in two well‐differentiated steps. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3761–3770, 2000     

Non‐equilibrium phase behavior of diblock copolymer melts and binary blends in the intermediate segregation regime

The phase behavior of intermediately segregated (χN = 45) poly(ethylene)‐poly(ethylethylene) (PE–PEE) diblock copolymers and PE–PEE binary blends are characterized using transmission electron microscopy and small‐angle X‐ray scattering. Surprisingly, the preparation‐dependent, nonequilibrium phase behavior can be overwhelming even at this degree of segregation. A pure diblock with a poly(ethylene) volume fraction of f_PE = 0.46 exhibited coexisting lamellae and perforated layers when prepared using a precipitation technique, but contained only the lamellar morphology when solvent cast. This preparation dependence was more dramatic in binary diblock copolymer blends with average compositions of 〈f_PE〉 = 0.44, 0.46, and 0.48. Precipitated blends exhibited a microphase separated structure that was disordered and bicontinuous; however, solvent cast samples exhibited either a cylindrical, coexisting cylindrical and lamellar, or lamellar morphology. This nonequilibrium behavior is attributed to the high degree of segregation and the proximity to the cylinder/lamellae phase boundary. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2229–2238, 1999     

Depth profiling of latex blends of fluorinated and fluorine‐free acrylates with laser‐induced secondary mass spectrometry

We explored phase separation and self‐assembly of perfluoroalkyl segments at the surface of polymer films obtained from latices of semifluorinated acrylate copolymers and the corresponding latex blends of nonfluorinated and semifluorinated polyacrylates. With laser‐induced secondary mass spectrometry the fluorine distribution was measured after annealing above the minimum film‐forming temperature of the polymers up to a depth of several micrometers. Depth profiles of a semifluorinated acrylate homopolymer and latex blends thereof with fluorine‐free alkylacrylates with 25, 50, and 75 mol % semifluorinated acrylate as well as a copolymer comprised of alkyl acrylate and semifluorinated acrylate (50/50 mol %) were investigated. In the case of latex blends containing both semifluorinated polyacrylates and fluorine‐free or low‐fluorine polymers, self‐assembly accounted for enrichment of the perfluoroalkyl segments at the surface. Coatings exhibiting low surface energy and having a substantially reduced total fluorine content were obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 360–367, 2003     

Flexibilized styrene‐N‐substituted maleimide copolymers. I. Multiblock copolymers prepared from styrene‐maleimide telechelics and polytetrahydrofuran

Telechelic copolymers of styrene and different N‐substituted‐maleimides (SMIs) with a molecular weight of 2000–8000 g/mol were synthesized using the starved‐feed‐reactor technique and were nearly bifunctional when the monomer feed had a high styrene concentration. The COOH‐terminated rigid SMI blocks were polycondensated with OH‐terminated poly(tetrahydrofuran) (PTHF) blocks, with a molecular weight of 250–1000 g/mol, which are the flexible parts in the generated homogeneous multiblock copolymer. The entanglement density, which is closely related to the toughness of materials, increased in these flexible SMI copolymers (ν_e = 5.2 · 10²⁵ m⁻³) compared to the unflexibilized ones (ν_e = 2.4 · 10²⁵ m⁻³). The glass transition temperature of these flexibilized, single‐phase multiblock copolymers was still high enough to qualify them as engineering plastics. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3550–3557, 2000     

Miscibility and morphologies of poly(arylene ether phenyl phosphine oxide/sulfone) copolymer/vinyl ester resin mixtures and their cured networks

Nonreactive bisphenol A‐based poly(arylene ether triphenyl phosphine oxide/diphenyl sulfone) statistical copolymers and a poly(arylene ether triphenyl phosphine oxide) homopolymer, each having a number‐average molecular weight of about 20 kg/mol, were synthesized and solution‐blended with a commercial dimethacrylate vinyl ester resin. Free‐radical cured systems produced morphologies that were a function of both the amount of phosphonyl groups and the weight percentage of the copolymers. For example, highly hydrogen‐bonded poly(arylene ether phenyl phosphine oxide) homopolymer/vinyl ester resin mixtures were homogeneous in all proportions both before and after the formation of networks. Copolymers containing low amounts (≤30 mol %) of the phosphonyl groups displayed phase separation either before or during cure. The phase‐separated cured materials generally had phase‐inverted morphologies, such as a continuous thermoplastic copolymer phase and a particulate, discontinuous vinyl ester network phase, except for systems containing a very low copolymer content. The resin modified with a copolymer containing 30 mol % phosphine oxide comonomer showed improved fracture toughness, suggesting the importance of both phase separation and good adhesion between the thermoplastic polymer and the crosslinked vinyl ester filler phase. The results suggested that the copolymers with high amounts of phosphine oxide should be good candidates for interphase sizing materials between a vinyl ester matrix and high‐modulus carbon fibers for advanced composite systems. Copolymers with low amounts of phosphonyl groups can produce tough, vinyl ester‐reinforced plastics. The char yield increases with the concentration of bisphenol A poly(arylene ether phosphine oxide) content, suggesting enhanced fire resistance. The incorporation of thermoplastic copolymers sustains a high glass‐transition temperature but does not significantly affect the thermal degradation onset temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2409–2421, 2000     

Effects of the copolymer microstructure on the morphology of polyethylene–poly(ethylene‐co‐α‐olefin) blends

The effects of the copolymer microstructure on the morphology evolution in polyethylene/poly(ethylene‐co‐α‐olefin) blends were investigated. Microscopy revealed that the melt‐phase morphology, inferred from the solid‐state morphologies of annealed and quenched samples, was strongly affected by the copolymer structure, that is, the branch content and branch length. Higher molecular weight α‐olefin comonomer residues and residue contents in the copolymers led to faster coarsening of the morphology. The molecular weight of the polyethylene and the copolymers affected the coarsening rates of the morphology, principally through its influence on the melt viscosity. The effects of the molecular weight were largely explained by the normalization of the coarsening rate data with respect to the thermal energy and zero‐shear‐rate viscosity. Thus, the effect of the molecular weight on the compatibility of the blends was much smaller than the effects of the branch length and branch number. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 965–973, 2004     

Molecular mixing of incompatible polymers through formation of and coalescence from their common crystalline cyclodextrin inclusion compounds

We describe the successful mixing of polymer pairs and triplets that are normally incompatible to form blends that possess molecular‐level homogeneity. This is achieved by the simultaneous formation of crystalline inclusion compounds (ICs) between host cyclodextrins (CDs) and two or more guest polymers, followed by coalescing the included guest polymers from their common CD–ICs to form blends. Several such CD–IC fabricated blends, including both polymer1/polymer2 binary and polymer1/ polymer2/polymer3 ternary blends, are described and examined by means of X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, and solid‐state NMR to probe their levels of mixing. It is generally observed that homogeneous blends with a molecular‐level mixing of blend components is achieved, even when the blend components are normally immiscible by the usual solution and melt blending techniques. In addition, when block copolymers composed of inherently immiscible blocks are coalesced from their CD–ICs, significant suppression of their normal phase‐segregated morphologies generally occurs. Preliminary observations of the thermal and temporal stabilities of the CD–IC coalesced blends and block copolymers are reported, and CD–IC fabrication of polymer blends and reorganization of block copolymers are suggested as a potentially novel means to achieve a significant expansion of the range of useful polymer materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4207–4224, 2004     

Synthesis,characterization, and self‐assembly of comb‐dendronized amphiphilic block copolymers

Novel amphiphilic comb‐dendronized diblock copolymers composed of hydrophobic Percec‐type dendronized polystyrene block and hydrophilic comb‐like poly(ethylene oxide) grafted polymethacrylate P(PEOMA) block were designed and synthesized via two steps of atom transfer radical polymerization (ATRP). The comb‐like P(PEOMA) prepared by ATRP of macromonomers (PEOMA) with two different molecular weights (M_n = 300 and 475) were used to initiate the sequent ATRP of dendritic styrene macromonomer (DS). The molecular weights and compositions of the obtained block copolymers were determined by ¹H NMR analysis. The copolymers with relatively narrow polydispersities (1.27–1.38) were thus obtained. The bulk properties of comb‐dendronized block copolymers were studied by using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction (WAXD). Similar to dendronized homopolymers, the block copolymers exhibited hexagonal columnar liquid‐crystalline phase structure. By using such amphiphilic comb‐dendronized block copolymers as building blocks, the rich self‐assembly morphologies, such as twisted string, vesicle, and large compound micelle (LCM), were obtained in a mixture of CH₃OH and THF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4205–4217, 2008     

Organizing thermodynamic data obtained from multicomponent polymer electrolytes: Salt‐containing polymer blends and block copolymers

The objective of this review is to organize literature data on the thermodynamic properties of salt‐containing polystyrene/poly(ethylene oxide) (PS/PEO) blends and polystyrene‐b‐poly(ethylene oxide) (SEO) diblock copolymers. These systems are of interest due to their potential to serve as electrolytes in all‐solid rechargeable lithium batteries. Mean‐field theories, developed for pure polymer blends and block copolymers, are used to describe phenomenon seen in salt‐containing systems. An effective Flory–Huggins interaction parameter, χ_eff , that increases linearly with salt concentration is used to describe the effect of salt addition for both blends and block copolymers. Segregation strength, χ_effN , where N is the chain length of the homopolymers or block copolymers, is used to map phase behavior of salty systems as a function of composition. Domain spacing of salt‐containing block copolymers is normalized to account for the effect of copolymer composition using an expression obtained in the weak segregation limit. The phase behavior of salty blends, salty block copolymers, and domain spacings of the latter systems, are presented as a function of chain length, composition and salt concentration on universal plots. While the proposed framework has limitations, the universal plots should serve as a starting point for organizing data from other salt‐containing polymer mixtures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1177–1187     

Vanadium(V) complexes containing tetradentate amine trihydroxy ligands as catalysts for copolymerization of cyclic olefins

A series of vanadium(V) complexes bearing tetradentate amine trihydroxy ligands [NOOO], which differ in the steric and electronic properties, have been synthesized and characterized. Single crystal X‐ray analysis showed that these complexes are five or six coordinated around the vanadium center in the solid state. Their coordination geometries are octahedral or trigonal bipyramidal. In the presence of Et₂AlCl, these complexes have been investigated as the efficient catalysts for ethylene polymerization and ethylene/norbornene copolymerization at elevated reaction temperature and produced the polymers with unimodal molecular weight distributions (MWDs), indicating the single site behaviors of these catalysts. Both the steric hindrance and electronic effect of the groups on the tetradentate ligands directly influenced catalytic activity and the molecular weights of the resultant (co)polymers. Other reaction parameters that influenced the polymerization behavior, such as reaction temperature, ethylene pressure, and comonomer concentration, are also examined in detail. Furthermore, high catalytic activities of up to 3.30 kg polymer/mmol_V·h were also observed when these complexes were applied to catalyze the copolymerization of ethylene and 5‐norbornene‐2‐methanol, producing the high‐molecular‐weight copolymers (M_w = 157–400 kg/mol) with unimodal MWDs (M_w/M_n = 2.5–3.0) and high polar comonomer incorporations (up to 12.3 mol %). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1122–1132, 2010     

Co‐ and terpolymerization of ethylene,propylene, and higher α‐olefins with high propylene contents using metallocene catalysts

The copolymerization of propylene/ethylene and terpolymerization of propylene/ethylene/α‐olefins using long‐chain α‐olefins such as 1‐octene and 1‐decene have been carried out using EtInd₂ZrCl₂//methylaluminoxane. High concentrations of propylene and low concentrations of α‐olefins (near 2 mol % of the total olefin concentration in the liquid phase) were used. The effect of the ethylene concentration in copolymerizations of propylene/α‐olefins was studied at medium ethylene contents (12 and 40 mol % in the gas phase). The polymers were molecularly characterized by gel permeation chromatography‐multiangle laser light scattering, wide‐angle X‐ray scattering, Fourier transform infrared spectroscopy, and DSC analyses. The shorter α‐olefin studied (1‐octene) produced the highest improvement of activity in terpolymerization at 12 mol % ethylene in the gas phase. About 2 mol % of 1‐octene in the liquid phase increases the activity and decreases the molecular weight of terpolymers with respect to corresponding copolymers, whereas the mp is increased by almost 30 °C. The “termonomer effect” is less evident when higher amounts of ethylene are used. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1136–1148, 2001     

Effective interaction parameter between branched and linear polystyrene

Values of the effective interaction parameter (χ) between regular, long‐branched polystyrene chains and their linear analogues were measured with small‐angle neutron scattering for several star‐branched chains and one comb‐type polymer. The contribution to this interaction due to architecture alone increases monotonically with star functionality for the set of polymers studied here. The interaction appears to be less sensitive to variations in arm size than would be expected from fluctuation theory predictions by G. H. Fredrickson, A. Liu, and F. S. Bates (Macromolecules 1994, 27, 2503) for a purely entropic interaction due to architecture. The change in χ with the volume fraction of the star in the blend is in agreement with the theory, however. The magnitudes of the interaction in the star/linear blends are small enough that bulk phase separation is unlikely, whereas that in the comb/linear blend is about 20 times higher for the same number of arms. Thus, bulk phase separation can be readily expected for comb/linear blends at commercially relevant values of molecular weights. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2549–2561, 2001     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). II. Effect of poly(phenylene sulfide) homopolymer solubilization of PPS‐graft‐PET copolymer on morphology and crystallization behavior

The morphology and crystallization behavior of poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) blends compatibilized with graft copolymers were investigated. PPS‐blend‐PET compositions were prepared in which the viscosity of the PPS phase was varied to assess the morphological implications. The dispersed‐phase particle size was influenced by the combined effects of the ratio of dispersed‐phase viscosity to continuous‐phase viscosity and reduced interfacial tension due to the addition of PPS‐graft‐PET copolymers to the blends. In the absence of graft copolymer, the finest dispersion of PET in a continuous phase of PPS was achieved when the viscosity ratio between blend components was nearly equal. As expected, PET particle sizes increased as the viscosity ratio diverged from unity. When graft copolymers were added to the blends, fine dispersions of PET were achieved despite large differences in the viscosities of PPS and PET homopolymers. The interfacial activity of the PPS‐graft‐PET copolymer appeared to be related to the molecular weight ratio of the PPS homopolymer to the PPS segment of the graft copolymer (M_H/M_A). With increasing solubilization of the PPS graft copolymer segment by the PPS homopolymer, the particle size of the PET dispersed phase decreased. In crystallization studies, the presence of the PPS phase increased the crystallization temperature of PET. The magnitude of the increase in the PET crystallization temperature coincided with the viscosity ratio and extent of the PPS homopolymer solubilization in the graft copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 599–610, 2000     

Control of droplet size of polymer–diluent blends through thermally induced phase separation

The effects of process conditions and molecular structure of polymer and diluent on the droplet size of membranes formed by thermally induced phase separatiom (TIPS) process were examined. The observed upper critical solution temperature–type phase boundaries of nylon‐12 blended with poly(ethylene glycol) (PEG) and nylon 12 diluted with poly(ethylene glycol) dimethyl ether (PEGDE) and their interaction energy densities calculated using the Flory–Huggins theory suggest that the nylon‐12/PEGDE blends are less stable than the nylon‐12–PEG blends. Infrared spectra confirmed that the difference in phase stability might come from specific interactions of the hydroxyl terminal groups of PEG with the amide groups from nylon‐12, which are not be feasible in the nylon‐12–PEGDE blends. The phase stability of diluent PEG blended with various nylons that are different in the number of methyl groups in the repeat unit was ranked in the order of: nylon‐6–PEG blend < nylon‐12–PEG blend < nylon‐11–PEG blend. We also noted that the phase‐separated droplets grew by both coalescence and the Oswald ripening process after the onset of phase separation. As a result, the cubic exponent of average droplet radius (R³) plotted against time satisfied the linear relationship. As the blends became less stable, the droplet growth rate increased and larger equilibrium droplets formed at a constant quenching depth. The TIPS membranes with desired pore structure could be prepared by controlling the molecular structure of components as well as by varying processing conditions such as quenching depth and annealing time. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3042–3052, 2000     

Kinetics of ethylene polymerization reactions with chromium oxide catalysts

Principal kinetic data are presented for ethylene homopolymerization and ethylene/1‐hexene copolymerization reactions with two types of chromium oxide catalyst. The reaction rate of the homopolymerization reaction is first order with respect to ethylene concentration (both for gas‐phase and slurry reactions); its effective activation energy is 10.2 kcal/mol (42.8 kJ/mol). The r₁ value for ethylene/1‐hexene copolymerization reactions with the catalysts is ～30, which places these catalysts in terms of efficiency of α‐olefin copolymerization with ethylene between metallocene catalysts (r₁ ～ 20) and Ti‐based Ziegler‐Natta catalysts (r₁ in the 80–120 range). GPC, DSC, and Crystaf data for ethylene/1‐hexene copolymers of different compositions produced with the catalysts show that the reaction products have broad molecular weight and compositional distributions. A combination of kinetic data and structural data for the copolymers provided detailed information about the frequency of chain transfer reactions for several types of active centers present in the catalysts, their copolymerization efficiency, and stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5315–5329, 2008