Morphology control of sulfonated poly(ether ketone ketone) poly(ether imide) blends and their use in proton-exchange membranes

Polymer blends based on sulfonated poly(ether ketone ketone) (SPEKK) as the proton-conducting component and poly(ether imide) (PEI) as the second component were considered for proton-exchange membranes (PEMs). The PEI was added to improve the mechanical stability and lower the water swelling in the fuel cell environment. Membranes were cast from solution using N-methyl-2-pyrrolidone (NMP) and dimethylacetamide (DMAc). The ternary, polymer/polymer/solvent, phase diagram was determined to provide guidance on how to control the morphology during solvent casting of blend membranes.

For blends of SPEKK (ion-exchange capacity = 2 mequiv/g) with PEI as the minority component, the morphology consisted of dispersed particles of 0.5–6 μm. Larger particles were achieved by increasing the PEI content and/or lowering the casting temperature. High-temperature annealing after solution casting did not affect the morphology of blend membranes, due to the low mobility and compatibility of the two polymers.

The possible use of SPEKK/PEI blends in PEMs is discussed in terms of existing theories of ion transport in polymers.     

Rubber toughening of poly(ether imide) by modification with poly(butylene terephthalate)

Rubber toughening of poly(ether imide) (PEI) has been elusive up to now due to the high processing temperature of PEI, which leads to degradation of the rubber. In this study, by profiting from the miscibility between PEI and poly(butylene terephthalate) (PBT), and the low T_g of PBT, we prepared a blend by melt extrusion with 20 wt% PBT in an attempt to render it toughenable by decreasing its T_g and processing temperature. The PEI-rich blend was subsequently mixed with maleic anhydride (0.9 wt%) grafted poly(ethylene-octene) copolymer (mPEO) up to 30 wt%. The decrease in T_g and processing temperature resulted in no observable degradation of the mPEO, and to the formation of a homogeneous morphology of rubber particles with a fine particle size, indicating that compatibilization was achieved. Upon rubber addition, stiffness decreased, while a very large toughness increase occurred with only 15% mPEO (impact strength more than 10-fold that of the PEI-PBT matrix). Upon observation of the fracture surface, the increase in impact strength was attributed partially to the cavitation and debonding of the rubber particles, and mostly to the deformation and yielding of the PEI-PBT matrix.     

Structure and mechanical properties of blends of poly(ether imide) and an amorphous polyamide

Biphasic poly(ether imide)/poly(trimethyl hexamethylene terephthalamide) blends were obtained by injection moulding through the full composition range both with and without previous extrusion mixing. The extruded blends showed an improved performance, as the T_gs of the two amorphous phases changed and the changes were larger than those of directly injected blends. The T_g changes indicate the presence of the two components in the two phases of the extruded blends. The consequent low interfacial tension is proposed as the reason for the observed generally fine particle size (typically 0.3 μm). Both characteristics led to mostly ductile materials. The modulus of elasticity and the yield stress were slightly below those predicted by the rule of mixtures. As this was due to a lower orientation in the blends, both properties could improve through a change of the processing parameters. The increase in impact strength over that of pure PEI, and particularly, the sudden processability increase (35% torque decrease) upon a-PA addition, led to compatible blends that, as in the case of the 90/10 composition, could be a polymeric material alternative to unmodified PEI.     

Reaction-induced miscibility in blends comprised of bisphenol-A polycarbonate and poly(trimethylene terephthalate)

The inherent miscibility and effects of reaction-induced changes on the phase behaviour of blends of poly(trimethylene terephthalate) (PTT) with bisphenol-A polycarbonate (PC) were studied. The as-prepared (solution-cast) blends exhibited two well-spaced and separated glass transition temperatures (T_gs) and a heterogeneous phase-separated morphology, indicating an immiscible system. However, after annealing at high temperature (at 260 °C), the blends original two T_gs merged into one single T_g, and the annealed blends exhibited a homogeneous morphology, and turned from having a semicrystalline into having an amorphous nature upon extended annealing. The annealing-induced changes of phase behaviour in the blends were analyzed. The homogenization process of the blends upon heating is attributed to chemical transreactions between the PTT and PC chain segments, as evidenced with FT-IR characterization. The IR result showed a new aryl C-O vibration peak at 1,070 cm^–1 for the annealed blends, which is characteristic of an aromatic polyester structure formed from exchange reactions between PTT and PC. The transreactions between PTT and PC led to a random copolymer comprised of PC/PTT segments, which is believed to serve as a compatibilizer at the beginning stage of transreactions, but at later stage, the random copolymer became the main species of blends and turned to a homogeneous and amorphous phase.     

The miscibility of poly(vinyl alcohol)/poly(N-vinylpyrrolidone) blends investigated in dilute solutions and solids

Poly(vinyl alcohol) (PVA) (polymer A) and poly(N-vinylpyrrolidone) (PVP) (polymer B) are known to form a thermodynamically miscible pair. In the present study the conclusion on miscibility of PVA/PVP solid blends, confirmed qualitatively (DMTA, FTIR) and quantitatively (DSC, χ_AB = − 0.69 at 503 K) is compared with the miscibility investigations of PVA/PVP solution blends by the technique of dilute solution viscometry. The miscibility of the ternary (polymer A/ polymer B/ solvent) system is estimated on the basis of experimental and ideal values of the viscosity parameters k, b and [η]. It is found that the conclusions on miscibility or nonmiscibility drawn from viscosity measurements in dilute solution blends depend: (i) on the applied extrapolation method used for the determination of the viscosity interaction parameters, (ii) on the assumed definition of the ideal values and (iii) on the thermodynamic quality of the solvent, which in the case of PVA depends on its degree of hydrolysis. Hence, viscometric investigations of dilute PVA/PVP solution blends have revealed that viscometry, widely used in the literature for estimation of polymer-polymer miscibility can not be recommended as a sole method to presume the miscibility of a polymer pair.     

Glass transition,crystallization, and morphology relationships in miscible poly(aryl ether ketones) and poly(ether imide) blends

The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of T_g over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.     

Effects of miscible diluent of poly(ether imide) on ring-banded morphology of poly(trimethylene terephthalate)

The melting, crystallization, and self-packed ring patterns in the spherulites of miscible blends comprising poly(trimethylene terephthalate) (PTT) and poly(ether imide) (PEI) were revealed by optical, scanning electron microscopies (PLM and SEM) and differential scanning calorimetry (DSC). Morphology and melting behavior of the miscible PTT/PEI blends were compared with the neat PTT. Ringed spherulites appeared in the miscible PTT/PEI blends at all crystallization temperatures up to 220 °C, whereas at this high temperature no rings were seen in the neat PTT. A postulation was proposed, and interrelations between rings in spherulites and the multiple lamellae distributions were investigated. The specific interactions and the segregation of amorphous PEI were discussed for interpreting the morphological changes of 220 °C-melt-crystallized PTT/PEI samples. Interlamellar segregation of PEI might be associated with multiple lamellae in the spherulites of PTT/PEI blends; therefore, rings were more easily formed in the PTT/PEI blends at all crystallization temperatures. A postulated model of uneven lamellar growth, coupled with periodical spiraling, more properly describes the possible origin of ring bands from combined effects of both interactions and segregation between the amorphous PEI and PTT in blends.     

Synthesis and properties of phthalonitrile-terminated oligomeric poly(ether imide)s containing phthalazinone moiety

Three novel series of soluble and curable phthalonitrile-terminated oligomeric poly(ether imide)s containing phthalazinone moiety were synthesized from an excess amount of three dianhydrides and phthalazinone-based diamine, followed by reacting with 4-(3-aminophenoxy)phthalonitrile (APPh) in a two-step, one-pot reaction, respectively. The phthalonitrile oligomers containing phthalazinone moiety were cured in the presence of 4,4′-diaminodiphenylsulfone (DDS). The oligomers and the crosslinked polymers were characterized by DSC, FT-IR and elemental analysis. These phthalonitrile oligomers containing phthalazinone groups were found to be soluble in some aprotic solvents, such as chloroform, pyridine, m-cresol and N-methyl-2-pyrrolidone (NMP). The crosslinked polymers were insoluble in all solvents. The thermal properties of the oligomers and the crosslinked polymers were evaluated using DSC and TGA analysis. The phthalonitrile oligomers showed high glass transition temperatures (T_gs) in the range of 214-256 °C and high decomposition temperatures with 10% weight loss (T_d10%) ranging from 523 to 553 °C. The crosslinked polymers showed excellent thermal stability with the 10% weight loss temperatures ranging from 543 to 595 °C, but did not exhibit a glass transition temperature upon heating to 350 °C.     

Synthesis and characterization of new aromatic poly(ether imide)s and their gas transport properties

A series of processable fluorinated poly(ether imide)s (PIs) were synthesized by reacting a diamine monomer, 1,4-bis-[{2′-trifluromethyl 4′-(4″-aminophenyl)phenoxy}] benzene (HQA) with six different aromatic dianhydrides e.g., BPADA, 6FDA, ODPA, BPDA, BTDA and PMDA. The polyimides showed reasonably high glass-transition temperature (T_g up to 280 °C) and high thermal stability (T_d,10 up to 558 °C). The membranes of these polymers showed tensile strength up to 107 MPa with elongation at break up to 15%, low water absorption (0.61–1.29%), low dielectric constant (2.10–3.13 at 1 MHz) and high optical transparency (λ_cut-off up to 466 nm). The PI membrane prepared from 6FDA exhibited high permeability and permselectivity for O₂/N₂ (P_O2 = 11.8 and P_O2/P_N2 = 9.44) gas pair which eventually surpassed the present upper boundary limit drawn by L.M. Robeson.     

Synthesis and properties of poly(ether imide)s based on a benzonorbornane bis(ether anhydride)

A novel bis(ether anhydride) monomer, 3,6‐bis(3,4‐dicarboxyphenoxy)benzonorbornane dianhydride, was synthesized from the nitro displacement of 4‐nitrophthalonitrile with 3,6‐dihydroxybenzonorbornane in the presence of potassium carbonate, followed by the alkaline hydrolysis of the intermediate bis(ether dinitrile) and the cyclodehydration of the resulting bis(ether diacid). A series of poly(ether imide)s bearing pendant norbornane groups were prepared from the bis(ether anhydride) with various aromatic diamines via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by thermal imidization to the poly(ether imide)s. The inherent viscosities of the poly(amic acid) precursors were 0.81–1.81 dL/g. The poly(ether imide) with m‐phenylenediamine as a diamine showed good organosolubility. Most of the cast poly(ether imide) films have had high tensile strengths and moduli. The glass‐transition temperatures of these poly(ether imide)s, except for those from rigid p‐phenylenediamine and benzidine, were recorded between 211 and 246 °C by differential scanning calorimetry. The softening temperatures of all the poly(ether imide) films stayed within 210–330 °C according to thermomechanical analysis. No polymers showed significant decomposition before 500 °C in a nitrogen or air atmosphere. A comparative study of the properties with the corresponding poly(ether imide)s without pendant substituents was also made. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1712–1725, 2002     

Miscibility studies on blends of poly(phenylene oxide)/brominated polystyrene by viscometry

The viscosity behavior of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), brominated polystyrene (PBrS) and their blends at several compositions (25/75, 50/50, 75/25, 85/15) has been studied. The miscibility of this polymer system was investigated on the basis of the sign of the criteria Δb, α, ΔK, μ, and Δ[η] determined by viscosity. These investigations indicate that PPO/PBrS is miscible at the compositions of (75/25), (85/15) and completely immiscible at the compositions of (25/75), (50/50) in chloroform at 20 °C. Results from viscometry match very well those of DSC results cited in the literature.     

A new category of thermally stable poly(ether amide ether imide)s with increased solubility

Two new poly(ether amide ether imide)s (PEAEIs) were prepared from a new diamine (DA) containing ether, aliphatic, amide, naphthyl and pyridine functional groups that resulted flexible and thermally stable ultimate polymers. The DA was synthesized via two steps, starting from nucleophilic substitution reaction of 1,8‐diamino‐3,6‐dioxaoctane with 6‐chloronicotinoyl chloride in the presence of propylene oxide which, afforded dichloro‐diamide (DCDA) compound. In the second step for the preparation of DA, reaction of DCDA compound with 5‐amino‐1‐naphthol in the presence of K₂CO₃ was achieved. The new DA was then polycondensed with 2,2'‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride and pyromellitic dianhydride to produce PEAEIs. The precursor, monomer and obtained polymers were entirely characterized by FT‐IR and ¹H‐NMR spectroscopy and elemental analysis techniques. The physical properties of the polymers including solubility, thermal behavior, thermal stability, inherent viscosity, morphology and mechanical properties were studied. The new PEAEIs exhibited favorable balance of physical and thermal properties, and their solubility was improved without sacrificing their thermal stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Synergistic mechanical behaviour and improved processability of poly(ether imide) by blending with poly(trimethylene terephthalate)

Fully miscible poly(ether imide) (PEI)/poly(trimethylene terephthalate) (PTT) blends were obtained by melt mixing in an extruder followed by injection moulding. The viscosity of PEI, represented by the pressure at the extruder output, almost halved upon the addition of only 10% PTT, allowing the use of PEI in applications where either complex parts or thin sections must be moulded. The modulus of elasticity showed a synergistic behaviour which was absolute (modulus higher than that of any of the two components) in the blend with 10% PTT. This was attributed mainly to the decrease in specific volume upon blending. The additional absolute synergism in the yield stress of PEI‐rich blends and their ductile nature depict a set of properties that make these new materials attractive in a number of new applications. Copyright ­© 2003 John Wiley & Sons, Ltd.     

磺化聚醚酰亚胺/聚醚砜共混型质子交换膜的制备及其性能

以磺化聚醚酰亚胺(SPEI)和聚醚砜(PES)为原料, 采用溶液共混法成功制备出了SPEI/PES共混型质子交换膜,并经热重分析、AFM、SEM等对膜的结构和性能进行了表征. 结果表明, 共混膜较纯SPEI膜具有更高的热稳定性和较低的溶胀性; 在室温环境下, 共混膜在干态和湿态时均具有优异的机械性能; 与纯SPEI膜相比, 共混膜的形态结构更为致密, 这将有利于降低甲醇的渗透性. 采用交流阻抗法和隔膜扩散法分别考察了膜的质子传导性和阻醇性能, 对于共混质量比为50/50的膜来说, 其质子传导率达到了5.5 mS·cm-1的水平, 能满足质子交换膜的需求, 但其甲醇渗透系数明显降低, 仅为市用Nafion 112膜的5%, 这表明该共混膜有望作为一种新型的直接甲醇燃料电池用质子交换膜.     

Glass transition and miscibility in blends of two semicrystalline polymers: Poly(aryl ether ketone) and poly(ether ether ketone)

Binary melt‐blended mixtures of two aryl ether ketone polymers (i.e., a new poly(aryl ether ketone) (code name PK99) and poly(ether ether ketone) (PEEK), have been studied. Polymer miscibility in glassy amorphous (or melt) domains has been demonstrated for the binary blend comprising of two aryl‐ether‐ketone‐type semicrystalline polymers. Composition‐dependent, single T_g was observed within full composition range in the PK99/PEEK blends, and the narrow T_g breadth also suggests that the scale of mixing was fine and uniform. To better resolve any possible overlapping T_g's, physical aging was imposed on a comparison set of blend samples for the purpose of improving detectability of overlapped multiple transitions if existing. The result still showed one single T_g. The relative sharp T_g and lack of cloud point transition suggest that the scale of molecular intermixing is good. Phase homogeneity was further confirmed using optical and scanning electron microscopy. The X‐ray diffractograms suggest that isomorphism does not exist in the PK99/PEEK blends and that the crystal forms of the respective polymers remain distinct and unchanged by the miscibility in the amorphous region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1485–1494, 1999     

Compatibilized poly(ether imide)/LCP blends: drawing ability and mechanical properties of the ribbons

The effects of the addition of polyarylate (PAr) on the drawing ability of poly(ether imide) (PEI)/Rodrun liquid‐crystalline 5000 (Ro LC5000) (Ro) blends and on the mechanical properties of their ribbons were studied. The compatibilizing effect of the PAr led to an increase in the drawing ability of the blends, as seen by the fact that the maximum Ro content compatible with the drawing process increased from 15 to 30%. This may lead to new applications in the field of gas barrier materials. The presence of PAr also led to an increase in the adhesion between the two phases of the blends and consequent improved ductility. However, the very high modulus of elasticity and tensile strength in the direction of orientation (up to three‐fold those of the matrix) due to the less developed fibrillation were smaller than the corresponding values before compatibilization. These very large modulus of elasticity and tensile strength values and those perpendicular to the direction of orientation, which were similar to those of the matrix, led to a high anisotropy in the extruded ribbons that increased with the draw ratio (DR) and the Ro contents. The high mechanical properties of the ribbons may be used and the anisotropy diminished by layering the ribbons in, and perpendicular to, the direction of orientation, according to the expected external load. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis and characterization of hyperbranched aromatic poly(ether imide)s with terminal amino groups

We synthesized an AB₂‐type monomer, 4‐{4‐[di(4‐aminophenyl)methyl]phenoxy}phthalic acid, which contained one phthalic acid group and two aminophenyl functionalities. The direct self‐polycondensation of the AB₂‐type monomer in the presence of triphenylphosphite as an activator afforded a hyperbranched poly(ether imide) with a large number of terminal amino groups. This polymer was characterized with ¹H NMR and IR spectroscopy. The degree of branching of the hyperbranched poly(ether imide) was approximately 56%, as determined by a combination of model compound studies and an analysis of ¹H NMR spectroscopy integration data. The terminal amino groups underwent functionalization readily. The solubility and thermal properties of the resulting polymers depended on the nature of the chain end groups. In addition, the hyperbranched poly(ether imide) was grafted with polyhedral oligomeric silsesquioxane (POSS). Transmission electron microscopy analysis revealed that the grafted POSS molecules aggregated to form a nanocomposite material. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3726–3735, 2003     

Pore structure and glass transition temperature of nanoporous poly(ether imide)

The effect of nanopores on the glass transition temperature (T_g) of poly(ether imide) was studied with differential scanning calorimetry. Nanoporous poly(ether imide) samples were obtained through the phase separation of immiscible blends of poly(ether imide) and polycaprolactone diol and by the removal of the dispersed minor phase domains with a selective solvent. Microscopy and statistical methods were used to characterize the pore structure and obtain the pore structure parameters. The pore size was found to depend on the processing time and the initial blend composition, mainly because of phase-coarsening kinetics. A decrease in T_g was observed in the nanoporous poly(ether imide) in comparison with the bulk samples. The change in T_g was strongly influenced by the pore structure and was explained by the percolation theory. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3546–3552, 2006     

Poly(ether imide) membranes modified with poly(ethylene imine) as potential carriers for epidermal substitutes

Poly(ether imide) (PEI) membranes were modified with a linear low-molecular weight (PETIM_0.6) and a branched high-molecular weight poly(ethylene imine) (PETIM_60). The membrane surfaces became more hydrophilic and the zeta potentials were shifted from negative to positive zeta values after immobilisation of both PETIM. These measurements also indicated the presence of a swollen surface layer in the case of PETIM_60, while a regular structuring of the surface was observed with scanning force microscopy for PETIM_0.6. A human keratinocyte cell line HaCaT was cultured on the different membranes. It was found that HaCaT cell growth was stimulated by PETIM_0.6. Cells reached earlier confluence on this substratum, while their growth was inhibited on a PEI membrane modified with PETIM_60, which makes PEI membranes modified with PETIM_0.6 a promising material for in vitro culture of epidermal transplants.     

Miscibility and properties of poly(l-lactic acid)/poly(butylene terephthalate) blends

Binary blends of poly(l-lactide) (PLLA) and poly(butylene terephthalate) (PBT) containing PLLA as major component were prepared by melt mixing. The two polymers are immiscible, but display compatibility, probably due to the establishment of interactions between the functional groups of the two polyesters upon melt mixing. Electron microscopy analysis revealed that in the blends containing up to 20% of poly(butylene terephthalate), PBT particles are finely dispersed within the PLLA matrix, with a good adhesion between the phases. The PLLA/PBT 60/40 blend presents a co-continuous multi-level morphology, where PLLA domains, containing dispersed PBT units, are embedded in a PBT matrix. The varied morphology affects the mechanical properties of the material, as the 60/40 blend displays a largely enhanced resistance to elongation, compared to the blends with lower PBT content.