Novel aromatic and aromatic–aliphatic poly(thiourea‐amide)s for the extraction of toxic heavy metal ions

A series of novel aromatic and aromatic–aliphatic diamines [isophthaloyl bis(3‐(3‐aminophenyl)thiourea), terephthaloyl bis(3‐(3‐aminophenyl)thiourea), adipoyl bis(3‐(3‐aminophenyl)thiourea), sebacoyl bis(3‐(3‐aminophenyl)thiourea)] were synthesized starting from the dinitro compounds. Spectroscopic and elemental analyses were carried out for the structure elucidation of the monomers. Three series of poly(thiourea‐amide)s (PTAMs) bearing C?S groups were prepared through the condensation of new diamines with the diacid chlorides such as isophthaloyl, terephthaloyl and adipoyl chloride. The ensuing PTAMs were characterized using FTIR, ¹H‐NMR and ¹³C‐NMR techniques. Physical properties of the polymers such as solution miscibility, crystallinity, solution viscosity, molecular weight, and thermal properties were measured. Consequently, good organosolubility of these polymers was experiential in amide solvents as DMAc, DMF, DMSO and NMP. Moreover, PTAMs exhibited η_inh in the range of 0.92–1.56 dL/g and GPC measurements revealed M_w around 607 × 10²‐851 × 10². DSC served to envisage the glass transition temperatures (T_g) of poly(thiourea‐amide)s located between 232 and 258°C and the initial decomposition temperatures (T₀) probed by thermogravimetry were in the range of 305–419°C. Structure‐property relationship of these polymers was also studied. Eventually, solid?liquid extraction tests of the selected poly(thiourea‐amide)s systems revealed excellent results because these polymers show nearly 100% elimination of lead and mercury cations from water media. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Thermophysical property modifications in functional polymers via lanthanide trichloride hydrates

Fourteen water‐soluble trivalent metal chlorides from lanthanum to lutetium in the 1st‐row of the f‐block form complexes with poly(vinylamine) and increase the glass transition temperature from 57°C to well above 100°C at very low molar concentrations of the lanthanide. The large ionic radii of these hard‐acid cations allow several hard‐base amino sidegroups in the polymer to occupy sites in the first shell coordination sphere via ion‐dipole (i.e., electrostatic) interactions, which leads to microclustering of the ligands about a single metal center. The enhancement in the glass transition temperature is explained in terms of multi‐functional coordination crosslinklng. f‐Block salts induce larger increases in T_g, relative to transition metal‐complexes from the d‐block, however CoCl₂(H₂O)₆ performs comparably to some of the more efficient lanthanides. Blends of poly(vinylamine) and trimethoxysilyl‐propylpoly(ethylene imine)hydrochloride form complexes with europium(III) and exhibit synergistic single T_g response. Since lanthanides form very stable complexes with chelating (i.e., bidentate) oxygen ligands, it is possible to increase the elastic modulus of commercially important copolymers of ethylene and methacrylic acid via Eu³⁺ complexation with the carboxylate anion. This claim is verified by infrared spectroscopy. Temperature and pH‐sensitive applications for drug delivery and removal of contaminants from wastewater streams should increase the utility of these lanthanide complexes.     

Europium‐containing cholesteric liquid crystalline polymers in the side chain

Europium‐containing cholesteric liquid crystalline polymers were graft copolymerized using poly(methylhydrogeno)siloxane, cholesteryl 4‐(allyloxy)benzoate (M₁), cholesteryl acrylate (M₂), and a europium complexes monomer (M₃). The chemical structures of the monomers were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermo gravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. With an increase of europium complexes units in the polymers, the glass transition temperature (T_g) did not change significantly; the isotropic temperature (T_i) and mesophase temperature range (ΔT) decreased. All polymers showed typical cholesteric Grandjean textures, which was confirmed by X‐ray diffraction. The temperatures at which 5% weight loss occurred (T_d) were greater than 300°C for the polymers. The introduction of europium complexes units did not change the liquid crystalline state of polymer systems; on the contrary, the polymers were enabled with the significant luminescent properties. With Eu³⁺ ion contents ranging between 0 and 1.5 mol %, luminescent intensity of polymers gradually increased and luminescent lifetimes were longer than 0.45 ms for the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40866.     

Synthesis and characterization of novel optically active poly(amide–imide)s containing N,N′‐(pyromellitoyl)‐bis‐L‐valine diacid chloride and 5,5‐disubstituted hydantoin derivatives under microwave irradiation

Pyromellitic dianhydride (1,2,4,5‐benzenetetracarboxylic acid 1,2,4,5‐dianhydide) was reacted with L ‐valine in a mixture of acetic acid and pyridine (3:2) at room temperature, and then was refluxed at 90–100 °C, N,N′‐(pyromellitoyl)‐bis‐L ‐valine diacid was obtained in quantitative yield. The imide–acid was converted to N,N′‐(pyromellitoyl)‐bis‐L ‐valine diacid chloride by reaction with thionyl chloride. Rapid and highly efficient synthesis of a number of poly(amide–imide)s was achieved under microwave irradiation using a domestic microwave oven by polycondensation of N,N′‐(pyromellitoyl)‐bis‐L ‐valine diacid chloride with six different derivatives of 5,5‐disubstituted hydantoin compounds in the presence of a small amount of a polar organic medium that acts as a primary microwave absorber. A suitable organic medium was o‐cresol. The polycondensation proceeded rapidly, compared with conventional melt polycondensation and solution polycondensation and was almost completed within 8 min, giving a series of poly(amide–imide)s with inherent viscosities in the range 0.15–0.36 dl g^?1. The resulting poly(amide–imide)s were obtained in high yield and are optically active and thermally stable. All of the above compounds were fully characterized by Fourier‐transform infrared (FT‐IR) spectroscopy, elemental analysis, inherent viscosity (η_inh) measurements, solubility testing and specific rotation measurements. The thermal properties of the poly(amide–imide)s were investigated by using thermogravimetric analysis. Copyright © 2004 Society of Chemical Industry     

Palladium(II) complexes with polyphosphazene

An allylphenoxy-substituted polyphosphazene has been modified via inorganic chemical concepts. The transition metal salt is bis(acetonitrile)dichloropalladium(II). The coordination complexes have been characterized using acid-base solution chemistry, sol-gel phase transitions, thermomechanical property measurements and infrared spectroscopy. Solid complexes of polyphosphazene and PdCl₂ cannot be dissolved in the original solvent (i.e., tetrahydrofuran) used during sample preparation. These polymeric palladium complexes also cannot be disrupted by a stronger base, like triphenylphosphine. There is a monotonic increase in the glass transition temperature at higher concentrations of palladium chloride. T_g of the pure polymer increases by 21°C in the presence of 10 mol% palladium chloride. The increase in high-strain mechanical properties cannot be explained solely by a “filler effect.” At higher PdCl₂ concentrations, there is a direct correlation between the enhancement in T_g, higher mechanical fracture stress, and increased infrared absorbance @ 1092 cm^?1 because of the formation of a palladium-π-complex with allylic substituents in the phenoxy sidegroup. Palladium chloride relinquishes its acetonitrile ligands after dissolution in THF, and the vacant sites in the first-shell coordination sphere of the transition metal are occupied by these allylic substituents in the sidegroup. This produces interchain coordination crosslinks, which modify the thermomechanical properties of polyphosphazene/ PdCl₂ complexes.     

Polylactide/transition metal ion modified montmorillonite nanocomposite—a critical evaluation of mechanical performance and thermal stability

Polylactide (PLA) nanocomposite was prepared by melt blending of PLA and transition metal ion (TMI) adsorbed montmorillonite (MMT). PLA nanocomposite was characterized for mechanical performance, and the results revealed that the tensile modulus, flexural modulus, and impact strength were increased marginally. The nanocomposite was optimized at 5 wt% of TMI‐modified MMT (TMI‐MMT) loading. Thermogravimetric analysis displayed increase in onset of degradation temperature, and differential scanning calorimetry showed marginal increase in glass transition temperature (T_g) and melting temperature (T_m) in case of PLA nanocomposites, when compared with virgin PLA. The flammability testing of nanocomposites indicated good fire retardance characters. X‐ray diffraction patterns of TMI‐MMT and the corresponding nanocomposites indicated an intercalation of the metal ions into the clay interlayer. Fourier transform infrared spectroscopy analysis indicate formation of [Zn(EDA)₂]²⁺ and [Cu(EDA)₂]²⁺ complexes in the MMT interlayer. Dynamic mechanical analysis shows increase in glass transition temperature (T_g) and storage modulus (E′) in case of PLA nanocomposites reinforced with 5 wt% modified MMT. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Free‐standing hybrid anion‐exchange membranes for application in fuel cells

A series of free‐standing hybrid anion‐exchange membranes were prepared by blending brominated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (BPPO) with poly(vinylbenzyl chloride‐co‐γ‐methacryloxypropyl trimethoxy silane) (poly(VBC‐co‐γ‐MPS)). Apart from a good compatibility between organic and inorganic phases, the hybrid membranes had a water uptake of 32.4–51.8%, tensile strength around 30 MPa, and T_d temperature at 5% weight loss around 243–261°C. As compared with the membrane prepared from poly (VBC‐co‐γ‐MPS), the hybrid membranes exhibited much better flexibility, and larger ion‐exchange capacity (2.19–2.27 mmol g^?1) and hydroxyl (OH^?) conductivity (0.0067–0.012 S cm^?1). In particular, the hybrid membranes with 60–75 wt % BPPO had the optimum water uptake, miscibility between components, and OH^? conductivity, and were promising for application in fuel cells. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

This article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single T_g, indicating the formation of random copolymers. A slight deviation of the T_g for the copolymers and its complexes can be observed. The copolymer T_g is higher than the T_g value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Metal‐solvating and self‐association of amphiphilic polyamides containing poly(oxyethylene) blocks

An amphiphilic poly(ether amide) consisting of hydrophilic poly(oxyethylene) amide blocks was prepared from the copolymerization of sebacic acid and two poly(oxyalkylene) diamines including a poly(oxyethylene) diamine (POE‐amine at 2000 M_w) and a poly(oxypropylene) diamine (POP‐amine at 230 M_w). The copolymer was estimated to have an average molecular weight of 15,000 M_w (GPC) or approximately three hydrophilic POE segments per strain. The presence of POE segments rendered polymer hydrophilicity and complexing ability for Li⁺, K⁺, Ca⁺², Ni⁺², Pd⁺², and Cu⁺² salts. In particular, lithium perchlorate affected the copolymer to the greatest extent in enhancing electrostatic dissipation or reducing surface resistivity as low as 10^5.0 Ω/sq (cross‐sectional area) at 1/180 Li⁺/EO from 10^7.2 Ω/sq (without metal ion). In such a metal complexation, the copolymer showed a new POE segmental crystalline phase at a melting temperature between ?10.4 and ?14°C, accompanied with the metal‐free original phase of ?31°C. In static toluene/water, the metal ions had no effect on the copolymer surfactancy in lowering the interfacial tension, reaching 4.4 dyn/cm at a critical micelle concentration (cmc) of 0.01 wt %. When mixing toluene and water, the lithium or nickel ions were found to be detrimental to the emulsifying process. Without the metal ion, fine droplets at average sizes of 4.5–5.0 μm were observed in the copolymer/ toluene/water emulsification. These amphiphilic behaviors of the POE‐segmented polyamide with or without metal ions were explained by the competing noncovalent bonding interactions among POE/metal ion/water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 612–621, 2002     

Synthesis of poly(aryl ether sulfone)‐graft‐polystyrene and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] through atom transfer radical polymerization

A new graft copolymers poly(aryl ether sulfone)‐graft‐polystyrene (PSF‐g‐PS) and poly(aryl ether sulfone)‐graft‐[polystyrene‐block‐poly(methyl methacrylate)] (PSF‐g‐(PS‐b‐PMMA)) were successfully prepared via atom transfer radical polymerisation (ATRP) catalyzed by FeCl₂/isophthalic acid in N,N‐dimethyl formamide. The products were characterized by GPC, DSC, IR, TGA and NMR. The characterization data indicated that the graft copolymerization was accomplished via conventional ATRP mechanism. The effect of chloride content of the macroinitiator on the graft copolymerization was investigated. Only one glass transition temperature (T_g) was detected by DSC for the graft copolymer PSF‐g‐PS and two glass transition temperatures were observed in the DSC curve of PSF‐g‐(PS‐b‐PMMA). The presence of PSF in PSF‐b‐PS or PSF‐g‐(PS‐b‐PMMA) was found to improve thermal stabilities. © 2002 Society of Chemical Industry     

Segmented copolymers of uniform tetra‐amide units and poly(phenylene oxide) by direct coupling

Segmented copolymers with telechelic poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE) segments and crystallizable bisester tetra‐amide units (two‐and‐a‐half repeating unit of nylon‐6,T) were studied. The copolymers were synthesized by reacting bifunctional PPE with hydroxylic end groups with an average molecular weight of 3500 g/mol and bisester tetra‐amide units via an ester polycondensation reaction. The bisester tetra‐amide units had phenolic ester groups. By replacing part of the bisester tetra‐amide units with diphenyl terephthalate units (DPT), the concentration of tetra‐amide units in the copolymer was varied from 0 to 11 wt%. Polymers were also prepared from bifunctional PPE, DPT, and a diaminediamide (6T6‐diamine). The thermal and thermal mechanical properties were studied by DSC and DMA and compared with a copolymer with flexible spacer groups between the PPE and the T6T6T. The copolymers had a high T_g of 180–200°C and a melting temperature that increased with amide content of 220–265°C. The melting temperature was sharp with monodisperse amide segments. The T_m – T_c was 39°C, which suggests a fast, but not very fast, crystallization. The crystallinity of the amide was ～ 20%. The copolymers are semicrystalline materials with a high T_g and a high T_g/T_m ratio (> 0.8). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 512–518, 2007     

Synthesis and properties of new aromatic poly(ester‐imide)s derived from 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl) pyridine and various dihydroxy compounds

A novel class of wholly aromatic poly(ester‐imide)s, having a biphenylene pendant group, with inherent viscosities of 0.32–0.49 dL g^?1 was prepared by the diphenylchlorophosphate‐activated direct polyesterification of the preformed imide‐ring‐containing diacid, 4‐p‐biphenyl‐2,6‐bis(4‐trimellitimidophenyl)pyridine (1) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A reference diacid, 2,6‐bis(trimellitimido)pyridine (2) without a biphenylene pendant group and two phenylene rings in the backbone, was also synthesized for comparison purposes. At first, with due attention to structural similarity and to compare the characterization data, a model compound (3) was synthesized by the reaction of compound 1 with two mole equivalents of phenol. Moreover, the optimum condition of polymerization reactions was obtained via a study of the model compound synthesis. All of the resulting polymers were characterized by Fourier transform infrared and ¹H NMR spectroscopy and elemental analysis. The ultraviolet λ_max values of the poly(ester‐imide)s were also determined. All of the resulting polymers exhibited excellent solubility in common organic solvents, such as pyridine, chloroform, tetrahydrofuran, and m‐cresol, as well as in polar organic solvents, such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethyl sulfoxide. The crystalline nature of the polymers obtained was evaluated by means of wide‐angle X‐ray diffraction. The resulting poly(ester‐imide)s showed nearly an amorphous nature, except poly(ester‐imide) derived from 4,4′‐dihydroxy biphenyl. The glass transition temperatures (T_g) of the polymers determined by differential scanning calorimetry thermograms were in the range 298–342 °C. The 10% weight loss temperatures (T_10%) from thermogravimetric analysis curves were found to be in the range 433–471 °C in nitrogen. Films of the polymers were also prepared by casting the solutions. Copyright © 2006 Society of Chemical Industry     

Polyether‐amide segmented copolymers based on ethylene terephthalamide units of uniform length

Segmented copolymers were synthesized using the crystallizable bisesterdiamide segment (N,N′‐bis(p‐carbomethoxybenzoyl)ethanediamine) T2T‐dimethyl (a one‐and‐a‐half repeating unit of nylon 2,T) and poly(tetramethyleneoxide) segments. Poly(tetramethyleneoxide) (PTMO) is amorphous and has a low T_g. The segment length was varied from 650 to 2800 g/mol by extending PTMO₆₅₀ using dimethyl isophthalate. The polymers were synthesized in the melt, and test samples were prepared by injection molding. The melting behavior, as well as the torsion modulus spectrum as a function of temperature, were studied using DSC and DMA, respectively. The T2T‐PTMO polymers were found to have sharp glass (T_g) and flow transitions (T_fl), and the modulus at the rubbery plateau appeared to be virtually temperature independent. The T_g value was found to be independent of the diamide concentration, thus indicating that the T2T segments were fully crystallized. The T_fl was found to decrease with increasing soft segment length; this was ascribed to a “solvent” effect of the amorphous phase of the crystalline T2T units. The difference between the melting and crystallization temperatures was found to be low, thus suggesting that on cooling, there is a high rate of crystallization. When ethanediol was added as a T2T segment extender, amide‐ester‐amide segments were introduced. These amide‐ester‐amide segments form a separate lamellar phase with a much higher melting temperature (>300°C). It was found that the crystallization rate of the T2T units was enhanced by the presence of the amide‐ester‐amide segments, indicating that upon cooling, the crystallized amide‐ester‐amide segments form the nucleation sites for the nonextended T2T segments. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1173–1180, 2001     

Mechanical and chemical properties of poly(styrene‐isobutylene‐styrene) block copolymers: Effect of sulfonation and counter ion substitution

In this study, the mechanical and chemical properties of a series of sulfonated poly(styrene‐isobutylene‐styrene) (SIBS) block copolymers were evaluated using a combination of nanoindentation, dynamic mechanical analysis (DMA), elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR), water absorption, and small angle X‐ray scattering studies (SAXS). The materials properties were characterized as a function of the sulfonation percent in the block copolymers, as well as a result of the counter‐ion substitution with Mg²⁺, Ca²⁺, and Ba²⁺. Nanoindentation studies revealed that the elastic modulus (E) and hardness (H) increase with sulfonation up to a certain level, at which point, the effect of water content further hinders any mechanical reinforcement. The incorporation of counter‐ions increases E and H, but the results are dependent upon the size of the counter‐ion. DMA results showed that the polymer maintained the glass transition temperature (T_g) of the polyisobutylene (PIB) segment (?60°C) regardless of the sulfonation level or counter‐ion substituted. However, both the shoulder of the PIB T_g (?30°C), which was probably caused by a Rouse‐type motion, as well as the T_g of polystyrene (105°C) disappeared upon sulfonation. Counter‐ion substitution increased the storage modulus of the rubbery plateau, which is indicative of a stronger and more thermally stable crosslinked complex formation. Additional unique relaxations were observed with the counter‐ions, and could be attributed to the stretching/rotation of the S? O bond and the interaction of the cations with the oxygen in the sulfonic group. FTIR results also revealed a unique shifting of the asymmetric S? O band when counter‐ions were added. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40344.     

Preparation and characterization of poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones

The two poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones have been prepared via polycondensation reaction of di‐tert‐butyl adipate and di‐tert‐butyl fumarate with 2,2‐bis(p‐chloro dimethylsiloxy‐phenyl)propane to give tert‐butyl chloride as the condensate. The polymerizations were performed under nitrogen at 110°C for 24 h without addition of solvents and catalysts to obtain the poly(silyl ester)s with weight average molecular weights typically ranging from 5000 to 10,000 g/mol. Characterization of the poly(silyl ester)s included ¹H NMR and ¹³C NMR spectroscopies, infrared spectroscopy, ultraviolet spectroscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), gel permeation chromatography, and Ubbelohde viscometer. The glass transition temperatures (T_g) of the obtained polymers were above zero because of the introducing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones. The TGA/DTG results showed that the obtained poly(silyl ester)s were stable up to 180°C and the residual weight percent at 800°C were 18 and 9%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1937–1942, 2006     

Synthesis and properties of copolymers of poly(ether ketone ketone) and poly(ether amide ether amide ether ketone ketone)

Poly(aryl ether ketone)s (PAEKs) are a class of high‐performance engineering thermoplastics known for their excellent combination of chemical, physical and mechanical properties, and the synthesis of semicrystalline PAEKs with increased glass transition temperatures (T_g) is of much interest. In the work reported, a series of novel copolymers of poly(ether ketone ketone) (PEKK) and poly(ether amide ether amide ether ketone ketone) were synthesized by electrophilic solution polycondensation of terephthaloyl chloride with a mixture of diphenyl ether and N,N′‐bis(4‐phenoxybenzoyl)‐4,4′‐diaminodiphenyl ether (BPBDAE) under mild conditions. The copolymers obtained were characterized using various physicochemical techniques. The copolymers with 10–35 mol% BPBDAE are semicrystalline and have markedly increased T_g over commercially available poly(ether ether ketone) and PEKK due to the incorporation of amide linkages in the main chain. The copolymers with 30–35 mol% BPBDAE not only have high T_g of 178–186 °C, but also moderate melting temperatures of 335–339 °C, having good potential for melt processing. The copolymers with 30–35 mol% BPBDAE have tensile strengths of 102.4–103.8 MPa, Young's moduli of 2.33–2.45 GPa and elongations at break of 11.7–13.2%, and exhibit high thermal stability and good resistance to organic solvents. Copyright © 2010 Society of Chemical Industry     

Preparation and dynamic mechanical properties of poly(styrene‐b‐butadiene)‐modified clay nanocomposites

Polybutyl acrylate (PBA) was intercalated into clay by the method of multistep exchange reactions and diffusion polymerization. The clay interlayer surface is modified, and obtaining the modified clay. The structures of the clay‐PBA, clay‐GA (glutamic acid), and the clay‐DMSO (dimethyl sulfoxide) were characterized using X‐ray diffraction (XRD). The new hybrid nanocomposite thermoplastic elastomers were prepared by the clay‐PBA with poly(styrene‐b‐butadiene) block copolymer (SBS) through direct melt intercalation. The dynamic mechanical analysis (DMA) curves of the SBS/modified clay nanocomposites show that partial polystyrene segments of the SBS have intercalated into the modified clay interlayer and exhibited a new glass transition at about 157°C (T_g3). The glass transition temperature of polybutadiene segments (T_g1) and polystyrene segments out of the modified clay interlayer (T_g2) are about ?76 and 94°C, respectively, comparied with about ?79 and 100°C of the neat SBS, and they are basically unchanged. The T_g2 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay, and the T_g3 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay up to about 8.0 wt %. When the contents of the modified clay are less than about 8.0 wt %, the SBS‐modified clay nanocomposites are homogeneous and transparent. The T_gb and T_gs of the SBS‐clay (mass ratio = 98.0/2.0) are ?78.39 and 98.29°C, respectively. This result shows that the unmodified clay does not essentially affect the T_gb and T_gs of the SBS, and no interactions occur between the SBS and the unmodified clay. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1499–1503, 2002; DOI 10.1002/app.10353     

New generation of thermally stable and conducting poly(azomethine‐ester)s: nano‐blend formation with polyaniline

A new dihydroxy monomer, (E)‐1‐(4‐(4‐(4‐hydroxybenzylidene)thiocarbamoylaminobenzyl)phenyl)‐3‐(4‐hydroxybenzylidene)thiourea, was synthesized and polymerized with thiophene‐2,5‐dicarbonyl/terephthaloyl chloride. The structural characterization of the resulting polymers was carried out using spectral techniques (Fourier transform infrared and ¹H NMR) along with a physical property investigation. Novel polyesters are readily soluble in various amide solvents and possess high molar mass of 112 × 10³–133 × 10³ g mol^?1. The thermal stability was determined via 10% weight loss to be in the range 519–523 °C and the glass transition temperature was 286–289 °C. Electrically conducting poly(azomethine‐ester)‐blend‐polyaniline blends were prepared using mash‐blending and melt‐blending techniques. Materials obtained using the conventional melt‐blending approach generated an efficient conductive network compared with those produced by mash blending. Field emission scanning electron microscopy revealed a nano‐blend morphology for the melt‐blended system owing to increased physical interactions (hydrogen bonding and π–π stacking) between the two constituent polymers. Miscible blends of thiophene‐based poly(azomethine‐ester)‐blend‐polyaniline had superior conductivity (1.6–2.5 S cm^?1) and thermal stability (T₁₀ = 507 °C) even at low polyaniline concentration relative to reported thiophene/azomethine/polyaniline‐based structures. The new thermally stable and conducting nano‐blends could be candidates for various applications including optoelectronic devices. © 2012 Society of Chemical Industry     

Pure and complex nanostructures using poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole], carbon nanotubes and reduced graphene oxide for high‐performance polymer solar cells

Crystallization of poly[bis(triiso‐propylsilylethynyl) benzodithiophene‐bis(decyltetradecyl‐thien) naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT) was investigated in supramolecules based on carbon nanotubes (CNTs) and reduced graphene oxide (rGO) and their grafted derivatives. The principal peaks of PBDT‐TIPS‐DTNT‐DT crystals were in the range 3.50°–3.75°. By grafting the surface of the carbonic materials, the assembling of polymer chains decreased because of hindrance of poly(3‐dodecylthiophene) (PDDT) grafts against π‐stacking. The diameters of CNT/polymer and CNT‐g‐PDDT/polymer supramolecules were 160 and 100 nm. The rGO/polymer supramolecules had the highest melting point (T_m = 282 °C) and fusion enthalpy (ΔH_m = 25.98 J g^?1), reflecting the largest crystallites and the most ordered constituents. Nano‐hybrids based on grafted rGO (276 °C and 28.26 J g^?1), CNT (275 °C and 27.32 J g^?1) and grafted CNT (268 °C and 22.17 J g^?1) were also analyzed. T_m and ΔH_m values were significantly less in corresponding melt‐grown systems. The nanostructures were incorporated in active layers of PBDT‐TIPS‐DTNT‐DT:phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) solar cells to improve the photovoltaic features. The best results were detected for PBDT‐TIPS‐DTNT‐DT:PC₇₁BM:rGO/polymer systems having J_sc = 13.11 mA cm^?2, fill factor 60% and V_oc = 0.71 V with an efficacy of 5.58%. On grafting the rGO and CNT, efficiency reductions were 12.01% (5.58%–4.91%) and 9.34% (4.07%–3.69%), respectively. © 2019 Society of Chemical Industry