Orientation and relaxation study of polystyrene: Polystyrene/poly(phenylene oxide) blends

Polarization modulation infrared linear dichroism has been used to study the molecular orientation and relaxation of polystyrene/poly(2,6‐dimethyl 1,4‐phenylene oxide) (PS/PPO) miscible blends, containing up to 20% PPO, during and after a rapid uniaxial deformation above T_g. In general, it is found that both the PS and PPO chain orientation functions increase with stretching rate and PPO content, and decrease with temperature. For all blends investigated, between T_g + 5 and T_g + 13 °C, the relaxation occurs at the same rate for PS and PPO and, therefore, the relaxation times calculated are similar indicating, under those conditions, a strong relaxation coupling between the two polymers at both short and long times. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1405–1415, 2000     

Interfacial profiles of miscible poly(4‐trimethylsilylstyrene)/polyisoprene bilayer films

Compositional profiles of bilayer films in the direction normal to the interfaces have been investigated by neutron reflectivity measurements and analyzed with mean field theory. The bilayer films were prepared with poly(4‐trimethylsilylstyrene) (PTMSS) and polyisoprene (PI), which constitute a miscible polymer pair and whose blends show phase separation at the lower critical solution temperature (LCST) by heating. Because we can accurately control the degree of polymerization of component polymers and can adjust the Flory–Huggins interaction parameter, χ, with the temperature, T, according to the relationship χ = 0.027–9.5/T, the phase behavior and the interfacial structure of PTMSS and PI are predictable by mean field theory. When the bilayer films of PTMSS and PI were set at 90 °C, which is a temperature below the LCST, diffusion at the interface was observed, and the original interface disappeared in several hours; this supports the idea that the polymer pair is miscible. No clear interfaces were identified below the LCST, whereas broad interfaces, compared with that of the strong segregation pairs, were observed above the LCST. The compositions of each layer are consistent with that of the coexisting phase in the polymer blends, and the interfacial widths agree well with the theoretical prediction considering the effect of capillary waves. In addition, all annealed films have a thin surface layer of PTMSS corresponding to surface segregation induced by the lower surface energy of PTMSS (with respect to that of PI). Thus, the interfacial profiles of PTMSS/PI bilayer films have been totally prospected in the framework of mean field theory. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1486–1494, 2005     

Synthesis and characterization of poly(phenylene oxide) graft copolymers by atom transfer radical polymerizations

A series of comb-like poly(phenylene oxide)s (PPO) graft copolymers with controlled grafting density and length of grafts were synthesized by atom transfer radical polymerization (ATRP). The α-bromo-poly(2,6-dimethyl-1,4-phenylene oxide)s (BPPO) were used as macroinitiators to polymerize vinyl monomers and the graft copolymers carrying polystyrene (PS), poly(p-acetoxystyrene) (PAS), and poly(methyl methacrylate) (PMMA) as side chains were synthesized and characterized by NMR, FTIR, GPC, DSC and TGA. The composition-dependent glass-transition temperatures (T_g) of PPO-g-PS exhibited good correlation with theoretical curve in Couchman equations except for the cases of low PS content (<40 mol%) copolymers in which a positive deviation was observed due to enhanced molecular interactions. The increase in monomer/initiator ratio led to the increase of degree of polymerization and the decrease of polydispersity. Despite the immiscibility nature between PPO and PMMA, the PPO-g-PMMA exhibited enhanced compatibilization as apparent single T_g in a wide temperature window throughout various compositions revealing an efficient segmental mixing on a molecular scale due to grafting structure.     

以离子-离子相互作用增强共混相容性Ⅰ.聚苯醚离聚体/聚(苯乙烯-乙烯吡啶)共混体系

本文从溶液行为和固体热行为对聚（2，6-二甲基1，4-苯醚）（PPO）离聚体（磺化聚苯醚或接化聚苯醚）／聚（苯乙烯-4-乙烯吡啶）（PS－VP）共混物进行了研究。DSC研究表明磺化度为7．7％mol的SPPO／PS－VP和羧化度为15％molCPPO炉S－VP在整个组成范围都是相容的。溶液行为研究表明，与对应的PPO／PS－VP共混物相比，这两个系列的共混物都表现出较高的比浓粘度。这是由于聚苯醚离聚体上的酸基发生质子转移，两组分间强烈的离子-离子相互作用导致分子间的络合，从而使比浓粘度的提高，也正是这种离子-离子相互作用使得这两对共混物完全相容。     

Gas transport properties of soluble poly(phenylene sulfone imide)s

Gas transport of helium, hydrogen, carbon dioxide, oxygen, argon, nitrogen, and methane in three soluble poly(phenylene sulfone imide)s based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride (6FDA) has been investigated. The effects of increasing length of well-defined oligo(phenylene sulfone) units on the gas permeabilities and diffusivities were determined and correlated with chain packing of the polymers. Activation energies of diffusion and permeation were calculated from temperature-dependent time-lag measurements. The influences of the central group in the diamine moiety of 6FDA-based polyimides on physical and gas transport properties are discussed. The incorporation of a long oligo(phenylene sulfone) segment in the polymer backbone decreases gas permeability and permselectivity simultaneously. The decreases in permeability coefficients can be mainly related to decreases in diffusion coefficients. Changing the central group of diamine moiety from  S to  SO₂ leads to a 45–50% decrease in CO₂ and O₂ permeabilities without appreciable increase in the selectivities. This is considered to be due to the formation of charge transfer complexes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1855–1868, 1997     

Crystallization,thermal behavior,and compatibility of poly(ethylene oxide)/poly(propylene oxide) blends

Isothermal and nonisothermal crystallization kinetics of different poly(ethylene oxide)/poly(propylene oxide) blends were investigated by means of differential scanning calorimetry (DSC). Glass transition temperature of quenched samples have also been reported. Phase morphologies and poly(ethylene oxide) spherulite growth rates were analyzed by polarizing light transmission microscopy. Results show morphological changes along with regime transitions of poly(ethylene oxide) crystal growth. Kinetic analyses of the data suggest that, although the blend behaves as a noncompatible, phase-separated system, there exists a certain degree of interaction between polymer chains. © 1996 John Wiley & Sons, Inc.     

Interface development in polycarbonate/poly(methyl methacrylate) bilayer films

We report the effect of annealing over a range of temperatures and times on the mixing, stability, and interfacial width in thin bilayer films of bisphenol A–polycarbonate (PC) on deuterated poly(methyl methacrylate) (dPMMA). These bilayer films were highly stable when annealed at temperatures of up to 438 K, the temperature at which the degradation of the blends of these materials was first detectable by thermogravimetric analysis. At higher temperatures, dewetting of the PC upper layer of the film occurred at an increasing rate. Nuclear reaction analysis showed that the PC and dPMMA layers remained segregated. Neutron reflectometry data showed that the interfacial width between the two polymer layers grew rapidly from 0.5 nm for an unannealed sample to approximately 4.0 nm, the latter value being in good agreement with the predicted value for the interfacial width in the absence of any reaction. Extended annealing at 438 K and lower temperatures had no effect on the interfacial width, whereas at higher temperatures, the interfacial width increased to approximately 5.5 nm before the films became unstable. The broadening of the interface found at higher annealing temperatures was attributed to an increase in the miscibility of the polymers induced by the monomer from the unzipping of the dPMMA chains. There was no evidence of a thermally induced chemical reaction between the two polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2351–2362, 2001     

Optical and SAXS characterization of poly(phenylene sulfide) (PPS) oligomers

Previously reported oligomeric PPSs prepared via the melt reaction of sulfur with excess p-diiodobenzene have been examined by optical microscopy and small-angle x-ray scattering (SAXS) techniques. A transition was seen from lamellar crystals for longer chains in the PPS samples of this work to a different type, which probably are extended chain crystals, occurring at about 20 DP. Spherulitic growth was observed optically for 38.8 DP and above. SAXS data established 31.8 DP as the point where a long period peak was first observed. The lamellar thickness of these bulk crystallized samples was established as about 50 Å which corresponds to a DP of 10. Maximum intensity of the SAXS peak increased with oligomer DP indicating increasing crystal perfection. Because of the random nature of the crystallization process, in PPS the average oligomer chain must be longer than three times this lamellar thickness to allow for folding and a spherulitic growth habit. © 1994 John Wiley & Sons, Inc.     

Synthesis of poly(p‐phenylene) macromonomers and multiblock copolymers

Rigid‐rod poly(4′‐methyl‐2,5‐benzophenone) macromonomers were synthesized by Ni(0) catalytic coupling of 2,5‐dichloro‐4′‐methylbenzophenone and end‐capping agent 4‐chloro‐4′‐fluorobenzophenone. The macromonomers produced were labile to nucleophilic aromatic substitution. The molecular weight of poly(4′‐methyl‐2,5‐benzophenone) was controlled by varying the amount of the end‐capping agent in the reaction mixture. Glass‐transition temperatures of the macromonomers increased with increasing molecular weight and ranged from 117 to 213 °C. Substitution of the macromonomer end groups was determined to be nearly quantitative by ¹H NMR and gel permeation chromatography. The polymerization of a poly(4′‐methyl‐2,5‐benzophenone) macromonomer [number‐average molecular weight (M_n) = 1.90 × 10³ g/mol; polydispersity (M_w)/M_n = 2.04] with hydroxy end‐capped bisphenol A polyaryletherketone (M_n = 4.50 × 10³ g/mol; M_w/M_n = 1.92) afforded an alternating multiblock copolymer (M_n = 1.95 × 10⁴ g/mol; M_w/M_n = 6.02) that formed flexible, transparent films that could be creased without cracking. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3505–3512, 2001     

Thermal transitions and structure of epoxy networks based on α, ω‐diamino terminated poly(propylene oxide)‐block‐poly(ethylene oxide)‐block‐poly(propylene oxide) swollen in water

Thermal transitions in epoxy networks prepared by reaction of α, ω‐diamino terminated poly(propylene oxide)‐block‐poly(ethylene oxide)‐block‐poly(propylene oxide) and diglycidyl ether of brominated Bisphenol A, swollen in water, were studied by differential scanning calorimetry (DSC) in a broad temperature range (from ?100 °C to 20 °C). Networks of two different values of initial molar ratio of amino and epoxy groups were prepared, r (r = 1.00, 2.00), and swollen with different amounts of water up to equilibrium concentration values. The qualitatively different kinds of experimental thermograms have been obtained for two networks and classified according to the amount of water in the sample on the basis of the phase diagram of the system. Also, the concentration dependence of the curves in this diagram (glass transition, melting, and crystallization) as well as the fraction of noncrystallizable water supply some information about the morphology of the system. In this sense, the existence of a microphase separated structure of swollen networks is suggested. The structure consists of hydrophilic and hydrophobic domains and depends on the initial molar ratio of the reactive groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 699–708, 2005     

Preparation and application of dense poly(phenylene oxide) membranes in pervaporation

Dense flat-sheet membranes were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) using the casting solvents chloroform and 1,1,2-trichloroethylene. X-ray diffraction, tapping mode atomic force microscopy (TM-AFM), and contact angle studies were used to characterize the membranes. The surface energy and the solubility parameters of the PPO membranes were determined from the measured contact angles and compared with the predicted ones from the group contribution method. Swelling experiments and pervaporation separation of methanol from its mixture with ethylene glycol over the entire range of concentration, 0-100%, were conducted using these membranes. Flory-Huggins theory was used to predict the sorption selectivity. The results are discussed in terms of the solubility parameter approach and as function of the morphological characteristics of the membranes. It was found that PPO membranes prepared with chloroform exhibited better pervaporation performance than PPO membranes prepared with 1,1,2-trichloroethylene.     

Effects of the conductivity of sulfonated poly(phenylene oxide) lithium by the complexation of poly(ethylene oxide)

In the present paper, the structure and conductivity for the complex of sulfonated poly(phenylene oxide) lithium (SPPOLi) and poly(ethylene oxide) (PEG) were studied. Glass transition temperature change determined by differential scanning calorimeter analysis desmonstrated that the two components had some compatibility. X-ray diffraction showed that PEG could decrease the regularity of SPPOLi to some extent. The compatibility and PEG's effect on the regularity may be due to the interaction between the lithium ions of SPPOLi and the oxygen atoms of PEG. Under polarization by electric field, the bands between lithium ions and sulfonation groups relaxed. Meanwhile, the complexation of oxygen atoms could enhance the dissociation of the polymeric lithium salts. Then lithium ions were transported in the process of alternate complexing and decomplexing. The action between lithium ions and oxygen atoms could explain the improvement on the conductivity of SPPOLi.     

Characterization and demulsification of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers

Four poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) copolymers with different molecular weights and PPO/PEO composition ratios were synthesized. The characterization of the PEO-PPO-PEO triblock copolymers was studied by surface tension measurement, UV-vis spectra, and surface pressure method. These results clearly showed that the CMC of PEO-PPO-PEO was not a certain value but a concentration range, in contrast to classical surfactant, and two breaks around CMC were reflected in both surface tension isotherm curves and UV-vis absorption spectra. The range of CMC became wider with increasing PPO/PEO composition ratio. Surface pressure Pi-A curves revealed that the amphiphilic triblock copolymer PEO-PPO-PEO molecule was flexible at the air/water interface. We found that the minimum area per molecule at the air/water interface increased with the proportion of PEO chains. The copolymers with the same mass fractions of PEO had similar slopes in the isotherm of the Pi-A curve. From the demulsification experiments a conclusion had been drawn that the dehydration speed increased with decreased content of PEO, but the final dehydration rate of four demulsifiers was approximate. We determined that the coalescence of water drops resulted in the breaking of crude oil emulsions from the micrograph.     

Interfacial effect on confined crystallization of poly(ethylene oxide)/silica composites

The impact of nanoconfinement introduced by nanoparticles on polymer crystallization has attracted extensive attention because it plays an important role in the ultimate properties of polymer nanocomposites. In this study, interfacial and spatial confinement effects of silica (SiO₂) nanoparticles on the crystallization behaviors of poly(ethylene oxide) (PEO)/SiO₂ composites were systematically investigated by changing the size and concentration of SiO₂ in PEO matrix. The composites with high silica loadings exhibit two crystallization peaks of PEO as determined by differential scanning calorimetry. The first peak at 7–43 °C is related to the bulk PEO, while the second peak at ?20 to ?30 °C is attributed to the restricted PEO segments. Three‐layer (amorphous, interfacial, and bulk) model is proposed to interpret the confined crystallization of PEO/SiO₂ composites, which is supported by the results of thermogravimetric analysis and solid‐state ¹H nuclear magnetic resonance. In amorphous layer, most PEO segments are directly adsorbed on SiO₂ surface via hydrogen bonding. The interfacial PEO layer, which is nonuniform, is composed of crystallizable loops and tails extending from amorphous layer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 414–423     

Blends of poly(2,6–dimethyl–1,4–phenylene oxide) with styrene copolymers

Binary blends of poly(2,6–dimethyl–1,4–phenylene oxide) (PPE) with various styrene copolymers were investigated. Poly(styrene–co–acrylonitrile) (SAN), poly[styrene–co–(methyl methacrylate)] (SMMA), poly[styrene–co–(acrylic acid)] (SAA) and poly[styrene–co–(maleic anhydride)] (SMA) are only miscible with PPE when the amount of comonomer is rather small. From calculated binary interaction densities it can be concluded that the strong repulsion between PPE and comonomer limits miscibility. In blends of PPE with SAN, as well as with ABS, the inter-facial tension between the blend components is significantly reduced upon addition of polystyrene–block–poly–(methyl methacrylate) diblock copolymers (PS–b–PMMA) and polystyrene–block–poly (ethylene–co–butylene)–block–poly–(methyl methacrylate) triblock copolymers (PS–b–PEB–b–PMMA). They show a profound influence on morphology, phase adhesion and mechanical blend properties.     

Block copolymers of telechelic poly(phenylene sulfide) and semiaromatic thermotropic liquid crystalline polyester segments

We report the synthesis and characterization of copolymers comprising poly(phenyl sulfide) (PPS) blocks and semiaromatic thermotropic liquid crystalline polymer (TLCP) blocks. The copolymers, synthesized by melt-transesterification of dicarboxy-terminated poly(phenylene sulfide) with poly(ethylene terephthalate-co-oxybenzoate) (PET/OB), were characterized using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and polarized light optical microscopy (PLOM). The crystallizability and liquid crystalline properties of the copolymers are greatly influenced by the extent of interchange reactions, the mole percent of oxybenzoate with respect to the PET, the PPS : PET/OB weight ratio, and the reaction time. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2707–2713, 1998     

Interfacial properties and thermal stability of modified poly(m‐phenylene isophthalamide) thin films

Poly(m‐phenylene isophthalamide) (PMIA) is a resistant to high temperatures and chemically stable engineering material. The application as coatings and membranes, however, is limited by its poor interaction with other materials. In this report, we describe the molecular modification of PMIA through reaction with dimsyl sodium and 2‐iodine‐1‐ethanol. The substitution of 58% of amide hydrogen by ethanol (etOH) groups produces a material (MPMIA) able to develop regularly structured films on silicon substrate. The morphology of the films is dependent on the ionic strength of the precursory solution. MPMIA starts a degradation process by losing the etOH group. MPMIA has a better affinity with poly(p‐cresolformaldehyde) than with a pristine one, increasing the range of composition in which thermal stability and miscibility are observed. Thin films of these blends have different morphologies that vary from nanometric porous to two‐phase microstructured grains, according to the composition. Copyright © 2012 John Wiley & Sons, Ltd.     

Interpenetrating polymer networks of poly(2,6-dimethyl-1,4 phenylene oxide) and poly(urethane acrylate). I

Simultaneous full and pseudo- interpenetrating polymer networks of poly(2,6-dimethyl-1,4 phenylene oxide) (PPO) and a poly(urethane acrylate) (PUA) have been synthesized and characterized by differential scanning calorimetry, ultimate mechanical properties, and electron microscopy. No evidence of phase separation was detected in both the full and pseudo- PPO/PUA networks. The networks exhibited a single glass transition temperature at all the compositions studied. A maximum in tensile strength to break was observed at 25 PPO/75 PUA composition by weight percent.     

The effect of in situ-formed copolymers on the morphology of reactive poly(phenylene ether)/poly(amide-6) blends

Poly(phenylene ether) (PPE)/poly(amide-6) (PA6) blends are examined in light of the information provided by two-dimensional chromatography and chemorheology. Chromatography provides a snapshot of the blend composition in the finished material, while rheology presents us with a direct insight into the reactions taking place in the melt. Block copolymer formation is chromatographically confirmed for the blends prepared with a coupling agent, but also for the blend prepared without any coupling agent. No co-continuous morphology is observed by scanning electron microscope. Instead, a coarse structure of PPE droplets in the PA6 matrix is obtained for the blend prepared without coupling agent. This is explained by the combined effects of the low viscosity of PA6 and the inherently formed copolymers. The PPE domains are smaller in the blends prepared with the coupling agents. Their size is correlated with the copolymer formation, surface tension, and interphase relaxation time. The data evidence a complex system where reactions resulting in the formation of copolymer via coupling or grafting take place together with the extension of the PPE and condensation growth of the PA6 polymers.