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     

Liquid phase demixing in ferroelectric/semiconducting polymer blends: An experimental and theoretical study

This article describes a combined experimental and theoretical study on nanophase structure development as a result of liquid phase demixing in solution‐cast blends of the organic semiconductor poly(9,9′‐dioctyl fluorene) (PFO) and the ferroelectric polymer poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)). Blend layers (200 nm) are prepared by spin coating a 1:9 (w/w) PFO:P(VDF‐TrFE) blend solution in a common solvent on a poly(ethylenedioxy thiophene)/poly(styrene sulfonate) substrate. Owing to the pronounced incompatibility between the two polymers, a strong phase‐separated morphology is obtained, characterized by disk‐like nanodomains of PFO embedded in a P(VDF‐TrFE) matrix, as revealed by scanning electron microscopy. By varying the processing conditions, we find the average domain size and standard deviation to increase with spinning time. The considerable increase in domain size suggests the coarsening process not to be impeded by a steep rise in viscosity. This indicates solvent evaporation to be only moderate within the experimental time frame. The evolution of the observed phase morphology is modeled using ternary diffuse interface theory integrated with a modified Flory–Huggins (FH) treatment of the homogeneous (bulk) free energy of mixing, to account for significant molecular differences between the active blend components. Using calculated FH interaction parameters, the model confirms the phase separation to occur via spinodal decomposition of the blend solution during spin coating, as suggested by experimental observations. The simulated phase morphologies as well as the modeled trends in domain growth and standard deviation compare favorably with the experimental data. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1255–1262, 2011     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010     

Thermoplastic blend demixing by a high‐pressure,high‐temperature process

The analysis of a thermoplastic polymer blend requires a precise separation of the blend components, which is usually performed by selective solvent extraction. However, when the components are high‐molecular‐weight polymers, a complete separation is very difficult. The use of fluids in near critical and supercritical conditions becomes a promising alternative to reach a much more precise separation. In this work, a method to separate reactive and physical blends from high‐molecular‐weight commercial polymers is proposed. Polyethylene (PE)/polystyrene (PS) blends were separated into their components with n‐propane, n‐pentane, and n‐heptane at near critical and supercritical conditions. The selectivity of each solvent was experimentally studied over a wide range of temperatures for assessing the processing windows for the separation of pure components. The entire PE phase was solubilized by n‐pentane and n‐heptane at similar temperatures, whereas propane at supercritical conditions could not dissolve the fraction of high‐molecular‐weight PE. The influence of the blend morphology and composition on the efficiency of the polymer separation was studied. In reactive blends, the in situ copolymer formed was solubilized with the PE phase by chemical affinity. The method proposed for blend separation is easy, rapid, and selective and seems to be a promising tool for blend separation, particularly for reactive blends, for which the isolation of the copolymer is essential for characterization © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2361–2369, 2005     

Phase separation temperatures in the ternary system polystyrene/poly(α-methyl styrene)/cyclopentane

Phase separation temperatures of the ternary system polystyrene (PS) (M_w = 1.67 × 10⁴)/poly(α-methyl styrene) (PαMS) (M_w = 9.0 × 10⁴)/cyclopentane with a blend ratio PS/PαMS = 55/45 have been determined over the polymer concentration range 0.02 ≤ ψ_{PS + PαMS} ≤ 0.52, where ψ _{PS + PαMS} is the segment fraction of polymer in ternary system. Phase separation temperatures for the upper critical separation in the ternary system decrease with increasing ψ _{PS + PαMS} over the range 0.1 ≤ ψ _{PS + PαMS} ≤ 0.52. The vapor—liquid equilibrium in this system with a blend ratio PS/PαMS=50/50 has been determined over the concentration range 0.925 ≤ ψ_{PS + PαMS} < 0.995 and the temperature range 60–100°C by the piezoelectric vapor sorption method. The polymer—polymer interaction parameters χ′₁₂ determined are positive except at 100°C and increase with increasing ψ _{PS + PαMS}. Values of χ′₁₂ extrapolated to zero solvent concentration are positive (0.0–1.3) over the temperature range measured. Phase separation behavior is discussed in terms of phase separation temperature in a ternary system and the polymer–polymer interaction parameter.     

Partial miscibility in a nylon‐6/nylon‐66 blend coalesced from their common α‐cyclodextrin inclusion complex

We successfully formed a series of inclusion complexes (ICs) between an α‐cyclodextrin (α‐CD) host and two kinds of guest polymers, nylon‐6 and nylon‐66. An attempt to achieve an intimate blend between nylon‐6 and nylon‐66 through the formation and dissociation of their common α‐CD IC was made. The formation of all nylon ICs was verified with wide‐angle X‐ray diffraction, differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) and cross‐polarized/magic‐angle‐spinning ¹³C NMR spectroscopy. The experimental results demonstrated that α‐CD could only host single nylon polymer chains in the IC channels, either nylon‐6 or nylon‐66 in their own complexes, and presumably either nylon in neighboring channels of their common IC. The IC‐coalesced blend of nylon‐6 and nylon‐66 was obtained after the removal of the host cyclodextrin from their common IC with dimethyl sulfoxide. The spectroscopic results (FTIR and ¹³C NMR) illustrated that there was a degree of intimate miscibility existing in the IC‐coalesced blend, but not in the solution‐cast physical blend, although X‐ray diffraction patterns showed that the crystal structure of the IC‐coalesced blend was similar to that of the physical blend. DSC thermal profiles suggested that nylon‐66 first formed crystals during coalescence and that the subsequent crystallization of nylon‐6 was greatly affected by the nylon‐66 crystallites because of the close proximity of the two components in portions of the coalesced blend. DSC observations also demonstrated that the melting of the coalesced blend did not lead to complete phase separation of the nylon‐6 and nylon‐66 components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1369–1378, 2004     

Ion‐pairing high‐performance liquid chromatography‐mass spectrometry of impurities and reduction products of sulphonated azodyes

An HPLC separation method with triethylammonium acetate mobile phase additive developed for the analysis of impurities in polysulphonated azo dyes provides good separation selectivity and compatibility with electrospray ionisation (ESI) mass spectrometry. The negative‐ion ESI mass spectra containing only peaks of deprotonated molecules [M–H]^– for monosulphonic acids, [M–xH]^x–, and sodiated adducts [M–(x + y)H + yNa]^x– for polysulphonic acids allow easy molecular mass determination of unknown impurities. Based on the knowledge of the molecular masses and of the fragment ions in the MS/MS spectra, probable structures of trace impurities in commercial dye samples are proposed. To assist in the interpretation of the mass spectra of complex polysulphonated azodyes, additional information can be obtained after chemical reduction of azodyes to aromatic amines. The structures of the non‐sulphonated reduction products can be determined by reversed‐phase HPLC/MS with positive‐ion atmospheric pressure chemical ionisation and of the sulphonated products by ion‐pairing HPLC/MS with negative‐ion ESI.     

Growth of Long Triisopropylsilylethynyl Pentacene (TIPS‐PEN) Nanofibrils in a Polymer Thin Film During Spin‐Coating

This study demonstrates the growth of long triisopropylsilyethynyl pentacene (TIPS‐PEN) nanofibrils in a thin film of a crystalline polymer, poly(ε‐caprolactone) (PCL). During spin‐coating, TIPS‐PEN molecules are locally extracted around the PCL grain boundaries and they crystallize into [010] direction forming long nanofibrils. Molecular weight of PCL and weight fraction (α) of TIPS‐PEN in PCL matrix are key factors to the growth of nanofibrils. Long high‐quality TIPS‐PEN nanofibrils are obtained with high‐molecular‐weight PCL and at the α values in the range of 0.03–0.1. The long nanofibrils are used as an active layer in a field‐effect organic transistor.

     

Precise synthesis of end‐functionalized thermosensitive poly(vinyl ether)s by living cationic polymerization

A series of poly(2‐methoxyethyl vinyl ether)s with narrow molecular weight distributions and with perfectly defined end groups of varying hydrophobicities was successfully synthesized by base‐assisting living cationic polymerization. The end group was shown to greatly affect the temperature‐induced phase separation behavior of aqueous solutions (lower critical solution temperature‐type phase separation) or organic solutions (upper critical solution temperature‐type phase separation) of the polymers. The cloud points were also influenced largely by the molecular weight and concentration of the polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and LCST‐type phase separation behavior in organic solvents of poly(vinyl ethers) with pendant imidazolium or pyridinium salts

Vinyl ether polymers with imidazolium or pyridinium salt pendants underwent sensitive lower critical solution temperature (LCST)‐type phase separation in organic media. Well‐defined poly(salts) were quantitatively prepared by reaction with corresponding imidazoles or pyridines and poly(2‐chloroethyl vinyl ether), which was synthesized by living cationic polymerization. For example, a solution of the homopolymer with butyl imidazolium salts exhibited a sharp and reversible transition in chloroform upon heating. Sensitive phase separation was also observed in nonpolar solvents, such as toluene, ethyl acetate, THF, containing a small amount of a good solvent, such as 1‐butanol (10–15 wt %). The dependency of the salt structures, molecular weight, and the concentration on this behavior was demonstrated. The cleavage of the hydrogen bond is a key factor in this phase separation, as indicated by DSC and ¹H‐NMR measurements. On increasing the temperature, the interaction between the polymer pendant and the solvent became weaker, hence the pendant–pendant interaction was, in turn, induced through the counter anion. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5724–5733, 2008     

Sensitive phase separation behavior of ultra-high molecular weight polyethylene in polybutene

Thermally induced phase separation (TIPS) has prompted a great deal of interest, especially as an effective approach to fabricate ultra-high molecular weight polyethylene (UHMWPE) microporous membranes. However, the existing utilized diluents for the TIPS process of UHMWPE suffer from environmental and health issues. Herein, we utilized low molecular weight polybutene (PB) bearing similar structure with liquid paraffin (LP) but inferior miscibility with UHMWPE relative to UHMWPE/LP blend, as a diluent for the TIPS process of UHMWPE. The phase separation behavior of UHMWPE/PB blends were investigated by the combination of rheological measurements, optical microscopy as well as differential scanning calorimeter (DSC). The results suggest that PB is fully miscible with UHMWPE at elevated temperature, but yielding a more sensitive phase separation behavior in respect to LP in TIPS process, because PB has weaker interaction with UHMWPE. The Jeziorny method analysis indicates that the crystallization mechanism of UHMWPE/LP blends is in line with that of UHMWPE/PB blends, which includes nucleation and growth as well as their dynamic competition. Moreover, compared to those of UHMWPE/LP blends, UHMWPE/PB blends display higher TIPS temperature and faster TIPS rate along with faster overall crystallization rate, further demonstrating that PB can accelerate phase separation rates and enhance the efficiency of TIPS process.     

High‐resolution MALDI‐TOF MS study on analysis of low‐molecular‐weight products from photo‐oxidation of poly(3‐hexylthiophene)

High‐resolution matrix‐assisted laser desorption/ionization (MALDI) time‐of‐flight mass spectrometry (TOF MS) was used for the analysis of the low‐molecular‐weight products from the photo‐oxidation of poly(3‐hexylthiophene) (P3HT) in solution and thin film. Eight new peak series were observed in the low‐mass range of the mass spectra of the products degraded in solution, and the formulas of the eight components were determined from the accurate mass. From SEC/MALDI‐TOF MS, two components were identified as the degraded products, and the other six components were derived from the fragmentation of the degraded products during the MALDI process. A mechanism for the formation of these components was proposed on the basis of the results of MALDI‐TOF MS. For the thin film degradation, a part of products in the solution degradation were observed, which supports that the oxidation of P3HT in solution and thin film proceeded in the same mechanism. This study shows that high‐resolution MALDI‐TOF MS is effective for the analysis of the low‐molecular‐weight products from P3HT photo‐oxidation and expected to be feasible for the degradation analyses of other polymers. Copyright © 2015 John Wiley & Sons, Ltd.     

Highly active,thermo‐responsive polymeric catalytic system for reuse in aqueous and organic CuAAC reactions

Tris‐(benzyltriazolylmethyl)amine (TBTA) has been immobilized onto a styrenic monomer and subsequently copolymerized with N‐isopropyl acrylamide (NIPAM) to afford catalytically active thermo‐responsive copolymers for copper assisted click chemistry. P(TBTA‐co‐NIPAM) copolymers were synthesized with incorporation of between 2 and 10 ligand units per chain and tuneable molecular weight (28–148 kDa). A combination of ¹H NMR spectroscopy, size exclusion chromatography (SEC) and elemental analysis (EA) confirmed the controlled synthesis of these polymers and allowed for quantification of the degree of TBTA‐functionalized monomer incorporation. After loading with copper(I) bromide, this homogeneous catalyst system was added to a water/ethyl acetate two‐phase system. Using this biphasic system aqueous click reactions could be performed at room temperature, while organic click chemistry could be performed above the cloud point temperature of the catalyst system. The polymer catalyst system could be regenerated via extraction by making use of its lower critical solution temperature (LCST)‐behavior, and then reused for further copper(I) catalyzed azide‐alkyne cycloaddition (CuAAC) reactions. While a reduced catalytic activity is observed as a result of copper leaching in aqueous click reactions, the recycling experiments in the organic phase demonstrated that this copolymer supported system allows for efficient recycling and reuse. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

应用高效液相色谱和电喷雾质谱联用技术分析鉴定车前草中的苯乙醇苷化合物

本文采用高效液相色谱与电喷雾质谱联用技术在线分析鉴定了车前草提取物中的三种苯乙醇苷化合物。实验采用反相C18色谱柱,0.2%的醋酸水溶液和乙腈梯度洗脱,车前草中的苯乙醇苷化合物得到很好的分离。在电喷雾质谱负离子条件下,获得了三种苯乙醇苷化合物的分子离子峰,分子量信息,进一步通过质谱的源内CID技术得到相应化合物的结构信息。通过得到的这些信息与文献中的已知化合物或标准品对照从而推断出化合物的结构。     

Melt‐flow‐induced phase morphologies of a high‐density polyethylene/poly(ethylene‐co‐1‐octene) blend

A blend of high‐density polyethylene and an elastomeric poly(ethylene‐co‐1‐octene) resin, containing 25 mol % octene and long‐chain branching, was phase‐separated in the melt under quiescent conditions. After melt flow, the blend had fine globular or interconnected phase morphologies that were interpreted as originating from the various stages of coarsening after liquid–liquid phase separation through spinodal decomposition. It was inferred that the miscibility of the blend was enhanced under melt flow. After cessation of flow, concurrent liquid–liquid and solid–liquid phase separation took place, resulting in the formation of an interpenetrating morphology comprising amorphous polyethylene, copolymer, and crystalline polyethylene. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 380–389, 2001     

Specific interactions and phase behavior of ternary poly(2‐vinylpyridine)/poly(N‐vinyl‐2‐pyrrolidone)/bisphenol A blends

Hydrogen‐bonding interactions between bisphenol A (BPA) and two proton‐accepting polymers, poly(2‐vinylpyridine) (P2VPy) and poly(N‐vinyl‐2‐pyrrolidone) (PVP), were examined by Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The Flory–Huggins interaction‐energy densities of BPA/P2VPy and BPA/PVP blends were determined by the melting point depression method. The interaction parameters for both BPA/P2VPy and BPA/PVP blend systems were negative, demonstrating the miscibility of BPA with P2VPy as well as PVP. The miscibility of ternary BPA/P2VPy/PVP blends was examined by DSC, optical observation, and solid‐state nuclear magnetic resonance spectroscopy. The experimental phase behavior of the ternary blend system agreed with the spinodal phase‐separation boundary calculated using the determined interaction‐energy densities. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1125–1134, 2002     

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) blend

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was investigated by optical microscopy (OM), light scattering (LS) method, and rheology. The blend had a lower critical solution temperature (LCST) of 112°C obtained by turbidity experiment using LS at a heating rate of 1°C/h. Three different blend compositions (critical 30/70 PS/PVME by weight) and two off‐critical (50/50 and 10/90)) were prepared. The rheological properties of each composition were monitored with phase‐separation time after a temperature jump from a homogeneous state to the preset phase‐separation temperature. For the 30/70 and 50/50 blends, it was found that with phase‐separation time, the storage and loss moduli (G′ and G″) increased at shorter times due to the formation of co‐continuous structures resulting from spinodal decomposition. Under small oscillatory shearing, shear moduli gradually decreased with time at longer phase‐separation times due to the alignment of co‐continuous structures toward the flow direction, as verified by scanning electron microscopy. However, for the 10/90 PS/PVME blend, the rheological properties did not change with phase‐separation times. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 889–906, 1999     

A π‐stacked and conjugated hybrid based on poly(N‐vinylcarbazole) postfunctionalized with terfluorene for stable deep‐blue hole‐transporting materials

The combination of π‐stacked with π‐conjugated building blocks offers an essential strategy to construct multifunctional organic semiconductors (MOSs) with the unique optoelectrical properties. Covalent hybrids can efficiently avoid the intrinsic phase‐separation defects in corresponding blend system. In this contribution, poly(vinylcarbazole) tethered with terfluorene, PVK‐TF, as a double‐channeled π‐stacked and π‐conjugated hybrid (SCH), has been constructed via Friedal‐Crafts click postmodification (FCCP). The chemical structure and optoelectrical property were determined by GPC, UV–vis, PL, TGA, DSC, and CV. Its PL spectra in the annealing thin film at N₂ atmosphere without low‐energy emission bands centered at the 530 nm indicates that no π‐stacks between carbazole and TF or among TFs dominate the whole condensed phase, which is in agreement with the intrachain T‐shaped π‐pitched motifs in molecular modeling simulation due to steric hindrance effect in complicated diarylfluorenes (CDAFs). A supporting prototype stable deep‐blue PLED was successfully obtained with an Internationale de l'Eclairage (CIE) coordinates of (0.20, 0.10) and a width at half maximum (FWHM) of about 60 nm at high current density of 100 mA/cm² (35 V). Deep‐blue PVK‐TF is a promising MOS for hole‐transporting and host materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5221–5229, 2009     

An intimate polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blend via coalescence from their common inclusion compound with γ‐cyclodextrin

In this study, we successfully report an intimate ternary blend system of polycarbonate (PC)/poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) obtained by the simultaneous coalescence of the three guest polymers from their common γ‐cyclodextrin (γ‐CD) inclusion compound (IC). The thermal transitions and the homogeneity of the coalesced ternary blend were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The observation of a single, common glass transition strongly suggests the presence of a homogeneous amorphous phase in the coalesced ternary polymer blend. This was further substantiated by solid‐state ¹³C NMR observation of the T_1ρ(¹H)s for each of the blend components. For comparison, ternary blends of PC/PMMA/PVAc were also prepared by traditional coprecipitation and solution casting methods. TGA data showed a thermal stability for the coalesced ternary blend that was improved over the coprecipitated blend, which was phase‐segregated. The presence of possible interactions between the three polymer components was investigated by infrared spectroscopy (FTIR). The analysis indicates that the ternary blend of these polymers achieved by coalescence from their common γ‐CD–IC results in a homogeneous polymer blend, possibly with improved properties, whereas coprecipitation and solution cast methods produced phase separated polymer blends. It was also found that control of the component polymer molar ratios plays a key role in the miscibility of their coalesced ternary blends. Coalescence of two or more normally immiscible polymers from their common CD–ICs appears to be a general method for obtaining well‐mixed, intimate blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4182–4194, 2004     

Effect of the liquid–liquid phase separation on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) and paraffin wax blend

The effect of liquid–liquid phase‐separation (LLPS) on the crystallization behavior and mechanical properties of poly(ethylene‐ran‐vinyl acetate) (EVA) with various amounts of vinyl acetate and paraffin wax blend was investigated. The blend of EVA‐H (9.5% vinyl acetate) and the wax became homogeneous at temperatures greater than its upper critical solution temperature (UCST) (98°C), and an LLPS was observed between UCST and the melting point of 88°C for EVA‐H in the blend. The existence of the LLPS is attributed to the relatively large amount of the hydrophilic component of vinyl acetate in EVA, although the molecular weight of the wax was just 560. However, LLPS did not occur for the EVA/wax blend when the content of vinyl acetate in EVA was less than 3%. This behavior was explained by using the Flory–Huggins lattice model with an effective interaction parameter. The degree of crystallinity of EVA‐H in the EVA‐H/wax blend, judged from a melting endothermic peak in differential scanning calorimeter (DSC) thermograms obtained during heating runs, decreased with increasing duration time in the LLPS region. The flexural modulus of the EVA/wax blend became maximum at certain blend composition (about 30 ∼ 40 wt % EVA depending upon the amount of vinyl acetate). This behavior can be explained by the fact that this blend composition has the largest relative degree of crystallinity of EVA measured by DSC and wide‐angle X‐ray scattering method. We found that the flexural modulus of the binder itself is directly related to that of a feedstock consisting of larger amounts of metal powder and the binder, which can help someone to develop a suitable binder system for a powder injection molding process. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1991–2005, 1999