Search

Poly(ether ether ketone) (PEEK) was found to form gels in the benign solvent 1,3-diphenylacetone (DPA). Gelation of PEEK in DPA was found to form an interconnected, strut-like morphology composed of polymer axialites. To our knowledge, this is the first report of a strut-like morphology for PEEK aerogels. PEEK/DPA gels were prepared by first dissolving PEEK in DPA at 320 °C. Upon cooling to 50 °C, PEEK crystallizes and forms a gel in DPA. The PEEK/DPA phase diagram indicated that phase separation occurs by solid–liquid phase separation, implying that DPA is a good solvent for PEEK. The Flory–Huggins interaction parameter, calculated as χ12 = 0.093 for the PEEK/DPA system, confirmed that DPA is a good solvent for PEEK. PEEK aerogels were prepared by solvent exchanging DPA to water then freeze-drying. PEEK aerogels were found to have densities between 0.09 and 0.25 g/cm3, porosities between 80 and 93%, and surface areas between 200 and 225 m2/g, depending on the initial gel concentration. Using nitrogen adsorption analyses, PEEK aerogels were found to be mesoporous adsorbents, with mesopore sizes of about 8 nm, which formed between stacks of platelike crystalline lamellae. Scanning electron microscopy and X-ray scattering were utilized to elucidate the hierarchical structure of the PEEK aerogels. Morphological analysis found that the PEEK/DPA gels were composed of a highly nucleated network of PEEK axialites (i.e., aggregates of stacked crystalline lamellae). The highly connected axialite network imparted robust mechanical properties on PEEK aerogels, which were found to densify less upon freeze-drying than globular PEEK aerogel counterparts gelled from dichloroacetic acid (DCA) or 4-chlorphenol (4CP). PEEK aerogels formed from DPA were also found to have a modulus–density scaling that was far more efficient in supporting loads than the poorly connected aerogels formed from PEEK/DCA or PEEK/4CP solutions. The strut-like morphology in these new PEEK aerogels also significantly improved the modulus to a degree that is comparable to high-performance crosslinked aerogels based on polyimide and polyurea of comparable densities. [ABSTRACT FROM AUTHOR]

This manuscript describes the synthesis and characterization of guanine and cytosine‐containing supramolecular copolymers, which are inspired from the guanine and cytosine nucleobase pair in deoxyribonucleic acid. Regioselective Michael‐addition allowed the efficient installation of the nucleobases on acrylate‐containing monomers, which enabled the preparation of a series of nucleobase‐functionalized acrylate and n‐butyl acrylate copolymers using conventional free radical copolymerization. Guanine‐containing copolymers exhibited superior thermal properties, thermomechanical performance, and more defined morphological structure than cytosine‐containing copolymer analogs due to the relatively strong guanine self‐association, thus expanding the potential applications for mechanically reinforced polymeric networks. Blending guanine‐ and cytosine‐containing copolymers formed a supramolecular structure through multiple hydrogen bonding between guanine and cytosine units. The supramolecular blend exhibited intermediate thermomechanical and morphological properties, which suggested that guanine and cytosine units were not fully associated in the random copolymer composition. This work provides valuable fundamental understanding of structure–property‐morphology relationships in acrylic copolymers with the presence of guanine‐cytosine self‐ and complementary interactions, suggesting new understanding in supramolecular design for enhanced mechanical and morphological properties. [ABSTRACT FROM AUTHOR]

In an effort to synthesize chemically recyclable thermoplastic elastomers, a redox‐switchable catalytic system was developed to synthesize triblock copolymers containing stiff poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran‐co‐cyclohexene oxide) (poly(THF‐co‐CHO) copolymer as the mid‐block. The orthogonal reactivity induced by changing the oxidation state of the iron‐based catalyst enabled the synthesis of the triblock copolymers in a single reaction flask from a mixture of monomers. The triblock copolymers demonstrated improved flexibility compared to poly(l‐lactic acid) (PLLA) and thermomechanical properties that resemble thermoplastic elastomers, including a rubbery plateau in the range of −60 to 40 °C. The triblock copolymers containing a higher percentage of THF versus CHO were more flexible, and a blend of triblock copolymers containing PLLA and poly(d‐lactic acid) (PDLA) end‐blocks resulted in a stereocomplex that further increased polymer flexibility. Besides the low cost of lactide and THF, the sustainability of this new class of triblock copolymers was also supported by their depolymerization, which was achieved by exposing the copolymers sequentially to FeCl3 and ZnCl2/PEG under reactive distillation conditions. [ABSTRACT FROM AUTHOR]

In an effort to synthesize chemically recyclable thermoplastic elastomers, a redox‐switchable catalytic system was developed to synthesize triblock copolymers containing stiff poly(lactic acid) (PLA) end blocks and a flexible poly(tetrahydrofuran‐co‐cyclohexene oxide) (poly(THF‐co‐CHO) copolymer as the mid‐block. The orthogonal reactivity induced by changing the oxidation state of the iron‐based catalyst enabled the synthesis of the triblock copolymers in a single reaction flask from a mixture of monomers. The triblock copolymers demonstrated improved flexibility compared to poly(l‐lactic acid) (PLLA) and thermomechanical properties that resemble thermoplastic elastomers, including a rubbery plateau in the range of −60 to 40 °C. The triblock copolymers containing a higher percentage of THF versus CHO were more flexible, and a blend of triblock copolymers containing PLLA and poly(d‐lactic acid) (PDLA) end‐blocks resulted in a stereocomplex that further increased polymer flexibility. Besides the low cost of lactide and THF, the sustainability of this new class of triblock copolymers was also supported by their depolymerization, which was achieved by exposing the copolymers sequentially to FeCl3 and ZnCl2/PEG under reactive distillation conditions. [ABSTRACT FROM AUTHOR]

A systematic investigations on the effect of sulfonic acid additives for the fabrication of thermally stable sulfonated poly(arylene ether sulfone) (PAES) composites for proton exchange membranes fuel cell applications were carried out. A uniform microstructure containing different concentration (1, 5 and 10 vol.%) of aromatic sulfonic acid additives (aniline‐2‐sulfonic acid (ASA), 3‐aminobenzenesulfonic acid (ABSA) and 3‐amino‐4‐hydroxy‐benzenesulfonic acid (AHBSA)) and biphenol‐based disulfonated poly(arylene ether sulfone) copolymer (PAES) as the matrix were successfully prepared. Phase segregation of the additives with sizes ranging from 1 to 2 μm was confirmed using scanning electron microscopy (SEM). Both thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) confirmed that additive derived PAES were thermally stable up to 400 °C. Proton conductivity of ASA‐PAES membranes was found to increase gradually with ASA concentration. Among all membranes PAES‐10 %ASA exhibited the highest conductivity of 0.123±0.01 S⋅cm−1 at 100 % relative humidity. However, PAES‐1 %ASA and PAES‐10 %ABSA membranes demonstrated the lowest leaching. Water uptake, ion exchange capacity and leaching parameters were correlated to additive concentration. This study will serve as a guide for the fabrication of PAES membranes with high concentration of sulfonated group in the polymer chain with enhanced thermal stability and proton conductivity. [ABSTRACT FROM AUTHOR]

The ability to quickly develop predictions of the service lifetime of plastic pipes at different load levels allows designers to choose the best plastic material and design pipe for a specific application. Additionally, it helps material producers to rapidly design, manufacture, test, screen, and modify the base polymeric material. The aim of this study is to introduce a combined experimental and analytical framework to develop accelerated lifetime estimates for semi‐crystalline plastic pipes which is sensitive to the structure, orientation, and morphology changes introduced by changing processing conditions. To accomplish this task, high density polyethylene (HDPE) is chosen as the exemplary base material and custom fixtures are developed to admit tensile and hoop burst tests on the as‐manufactured HDPE pipes. A pressure‐modified Eyring flow equation is employed to predict the rupture lifetime of HDPE pipes using the measured mechanical properties under uniaxial tensile and compression loading in different temperatures and strain rates. The method allows the prediction of pipe service lifetimes in excess of 50 years using experiments conducted over approximately 10 days instead of the traditional 13 months. POLYM. ENG. SCI., 60:879–888, 2020. © 2019 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

Structurally rigid copolyester thermoplastics were synthesized from 1,4‐cyclohexanedimethanol and the diesters dimethyl biphenyl‐4,4′‐dicarboxylate and dimethyl 2,6‐naphthalenedicarboxylate (DMN) via conventional melt transesterification. Conventional differential scanning calorimetry (CDSC) showed all compositions to exhibit multiple endotherms upon heating. Wide‐angle X‐ray diffraction analysis showed copolyester compositions to exhibit the crystalline structure of either the homopolyester Poly(1,4‐cyclohexylenedimethylene 2,6‐naphthalate) (PCN) or the homopolyester Poly(1,4‐cyclohexylenedimethylene 4,4′‐bibenzoate) (PCB), but not both simultaneously. Further thermal analysis using CDSC and fast DSC investigated the origin of the multiple endotherm behavior. While three endotherms are observed for low heating rates, the upper two endotherms appear to merge at heating rates about 1–5 °C s−1 and a single endotherm remains above heating rates about 10–50 °C s−1. While the behavior of the upper two endotherms is undeniably consistent with the mechanism of melting–recrystallization–remelting (MRR), we suggest that the low endotherm is likely associated with the melting of constrained secondary crystals, although MRR effects cannot be ruled out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 973–980 [ABSTRACT FROM AUTHOR]

This study proposes a novel method to mechanically characterize the performance of individual bonds in low‐density, thermomechanically bonded nonwoven fabrics. Commercial bicomponent, polyethylene/polypropylene (PE/PP), nonwoven fabric was laser cut into bowtie‐shaped specimens for uniaxial tensile testing so that the central region of each specimen contained an individual bond. Three groups, each composed of 20 specimens, were tested with their longitudinal axes oriented along the machine direction (MD), the cross direction (CD), and at 45° between these two directions (DD). Prior to testing, the intrinsic variation in areal density and fiber orientation in the region surrounding the individual bond were quantified via orientation and relative basis weight parameters. During testing, images of the specimens were acquired to determine the occurrence of fiber breakage, bond deformation, and bond cohesive failure. Maximum force, stiffness, and orientation parameters were found to be significantly different among the three specimen groups (p < 0.01) but the relative basis weight was not (p > 0.01). The stiffness and maximum load were linearly correlated with both the areal density and fiber orientation. Pre‐existing voids or windows within the bond lowered the maximum force for specimens with the longitudinal axes aligned with the MD. These voids had no influence on the maximum force achieved by the specimens aligned with the CD and DD. The bonds in these specimens were observed to deform less than the bonds in the specimens with the longitudinal axes aligned with the MD. The results indicate the importance of the fiber structure surrounding the bond on the tensile properties, deformation and failure mode of individual bonds within the nonwoven fabric. POLYM. ENG. SCI., 59:311–322, 2019. © 2018 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

Hydrogen bonding among nucleobase pairs serves as an efficient noncovalent interaction for designing supramolecular polymers with desired properties for pressure sensitive adhesives. Michael addition yielded acetyl-protected cytosine/guanine containing acrylic monomers with flexible spacers between the hydrogen bonding units and the acrylic backbone. Free radical polymerization of nucleobase-containing monomers afforded acetyl-protected cytosine/guanine homopolymers and random copolymers with n-butyl acrylate. Nucleobase incorporation significantly affected thermal, thermomechanical, rheological, morphological properties, and adhesive performance of polyacrylates. Guanine/cytosine-containing copolymers each exhibited a single glass transition (Tg) that increased with increasing nucleobase content. Self-association of acetyl cytosine and acetyl guanine units converted low Tg polyacrylates to physically crosslinked networks with mechanical integrity. Solution casting acetyl guanine-containing copolymers with 8 mol% or higher guanine content yielded free-standing films with microphase-separated morphologies. Acetyl cytosine-containing copolymers with 15 mol% or more cytosine formed free-standing films with less microphase-separation compared to the guanine copolymers. 1H NMR titration experiments established a 1:1 binding stoichiometry between acetyl cytosine and acetyl guanine monomers in CDCl3, similar to guanine-cytosine association. However, the acetyl protecting group hindered the formation of triple hydrogen bonding, resulting in double hydrogen bonding between acetyl cytosine and acetyl guanine with an intermediate binding strength comparable to their self-associations. Acetyl guanine-containing copolymers with 3 mol% acetyl guanine exhibited higher peel strength on stainless steel and higher extended service frequency range compared to cytosine-containing copolymers and various pressure sensitive adhesive controls. [ABSTRACT FROM AUTHOR]

We report the design of bioinspired, reversible supramolecular thermoplastic elastomers (TPEs) functionalized with ureido‐cytosine (UCyt) complementary quadruple hydrogen bonding (QHB) sites. The polymer contained a soft poly(n‐butyl acrylate) central block that imparted flexibility and two external, hard nucleobase‐containing blocks that contributed to structural integrity. In addition, the hard block with pendant QHB motifs served as efficient physical crosslinks to further enhance the thermomechanical performance, where the polymer service window extended up to 30 °C higher compared to the controls that bear dimeric hydrogen bonding units. The resulting UCyt copolymers also exhibited improved surface and bulk morphology, which self‐assembled into well‐ordered lamellar microstructures. Moreover, the polymer displayed an unexpected moisture‐resistant property with less than 1 wt % equilibrium moisture uptake even at 95% relatively humidity, which presumably correlated with its well‐ordered and densely‐packed morphology facilitated by strong hydrogen bonding. Variable temperature Fourier‐transform infrared spectroscopy experiments further confirmed the thermoreversibility of hydrogen bonding, indicating melt‐processablility and recyclability of the polymer. These physical properties verified quadruple bonding dominated behavior, and structure–property–morphology relationships suggest key design parameters for future TPEs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 13–23 ABA triblock copolymers functionalized with ureido‐cytosine (UCyt) pendant groups exhibit well‐ordered microstructures and enhanced moisture resistance compared to their cytosine‐functionalized precursors. Complementary quadruple hydrogen bonding between UCyt dimers serve as strong molecular stickers to direct self‐assembly, promoting molecular recognition, chain packing, and phase ordering of the polymers. [ABSTRACT FROM AUTHOR]

ABSTRACT: Reversible addition‐fragmentation chain transfer (RAFT) polymerization produced novel ABA triblock copolymers with associative urea sites within pendant groups in the external hard blocks. The ABA triblock copolymers served as models to study the influence of pendant hydrogen bonding on polymer physical properties and morphology. The triblock copolymers consisted of a soft central block of poly(di(ethylene glycol) methyl ether methacrylate) (polyDEGMEMA, 58 kg/mol) and hard copolymer external blocks of poly(2‐(3‐hexylureido)ethyl methacrylate‐co‐2‐(3‐phenylureido)ethyl methacrylate) (polyUrMA, 18‐116 kg/mol). Copolymerization of 2‐(3‐hexylureido)ethyl methacrylate (HUrMA) and 2‐(3‐phenylureido)ethyl methacrylate (PhUrMA) imparted tunable hard block Tg's from 69 to 134 °C. Tunable hard block Tg's afforded versatile thermomechanical properties for diverse applications. Dynamic mechanical analysis (DMA) of the triblock copolymers exhibited high modulus plateau regions (∼100 MPa) over a wide temperature range (−10 to 90 °C), which was indicative of microphase separation. Atomic force microscopy (AFM) confirmed surface microphase separation with various morphologies. Variable temperature FTIR (VT‐FTIR) revealed the presence of both monodentate and bidentate hydrogen bonding, and pendant hydrogen bonding remained as an ordered structure to higher than expected temperatures. This study presents a fundamental understanding of the influence of hydrogen bonding on polymer physical properties and reveals the response of pendant urea hydrogen bonding as a function of temperature as compared to main chain polyureas. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1844–1852 [ABSTRACT FROM AUTHOR]

ABSTRACT: Dimethyl itaconate and dicyclohexyl itaconate monomers are polymerized successfully for the first time via suspension polymerization. The obtained polymers possess significantly higher molecular weights and more narrow polydispersities compared to itaconate polymers prepared in solution or in bulk. The yields of these polymers from the suspension process are higher than the polymers synthesized from bulk. Solution cast films of both polymers were too brittle for mechanical properties characterization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46417. [ABSTRACT FROM AUTHOR]

1D ferroelectric nanostructures are promising for enhanced ferroelectric and piezoelectric performance on the nanoscale, however, their synthesis at the wafer scale using industrially compatible processes is challenging. In order to advance the nanostructure-based electronics, it is imperative to develop a silicon-compatible growth technique yielding high volumetric density and an ordered arrangement. Here, a major breakthrough is provided in addressing this need and ordered and close-packed single crystalline ferroelectric nanorod arrays, of composition PbZr0.52Ti0.48O3 (PZT), grown on commercial grade 3 in. silicon wafer are demonstrated. PZT nanorods exhibit enhanced piezoelectric and ferroelectric performance compared to thin films of similar dimensions. Sandwich structured architecture utilizing 1D PZT nanorod arrays and 2D reduced graphene oxide thin film electrodes is fabricated to provide electrical connection. Combined, these results offer a clear pathway toward integration of ferroelectric nanodevices with commercial silicon electronics. [ABSTRACT FROM AUTHOR]

Living anionic polymerization of 4-diphenylphosphino styrene ( DPPS) achieved unprecedented poly(S- b-I- b- DPPS) ABC triblock copolymers with predictable molecular weights and narrow polydispersities. In situ Fourier transform infrared spectroscopy probed the anionic polymerization, monitoring vinyl disappearance during sequential monomer addition for kinetic analysis. Varying the concentration of reinforcing, polystyrenic external blocks enabled diverse compositions with tunable thermomechanical properties and tailored morphology. Dynamic mechanical analysis confirmed the presence of microphase separation in the triblock copolymers and revealed a broad temperature range ( ca 100 oC) for a plateau region and onset of flow temperatures above 100 oC. Small-angle X-ray scattering and atomic force microscopy collectively revealed solid state morphologies of the triblock copolymers and probed phase separation at the nanoscale. Well-defined poly(S- b-I- b- DPPS) ABC triblock copolymers with tunable structure − property relationships now permit phosphorus-containing thermoplastic elastomers for emerging applications. © 2016 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

A two-step synthesis of epoxidation and carbonation afforded a hetero-functional AB monomer with cyclic carbonate and methyl ester (CC-ME) using plant oil-based methyl 9-decenoate and CO2. A unprecedented one-pot synthetic platform of CC-ME with 1,12-diaminododecane and poly(tetramethylene oxide) (PTMO)-based polyether diamine allowed synthesis of both nonsegmented poly(amide-hydroxyurethane) (PA12HU) and segmented PA12HU-PTMOs with varying polyether contents. 1H NMR spectroscopy confirmed complete conversion of cyclic carbonates and methyl esters to hydroxyurethanes and amides, respectively. Thermal analysis revealed distinctive thermal stability and transitions of PA12HU and PA12HU-PTMOs compared to their precursors and model oligomers. PA12HU and PA12HU-PTMOs were melt compression molded into semicrystalline, free-standing films, except for PA12HU-PTMO100 with 100% polyether diamine. PA12HU-PTMO100 was a viscous liquid with a glass transition temperature (Tg) of −64 °C and zero-shear melt viscosity of 449 Pa s. PA12HU formed a semicrystalline, rigid film with Tg of 11 °C. Polyether incorporation afforded creasable PA12HU-PTMO films with broad glass transitions near −50 °C. Thermal and thermomechanical analysis revealed significant phase-mixing of the hard and soft segments from annealed PA12HU-PTMO films. Polyether soft segments mixed with the amorphous hard segments, forming a miscible soft phase; crystallizable hard segments with ordered hydrogen bonding formed a hard phase. Surface morphological analysis of each PA12HU-PTMO film displayed ribbon-like, hard domains with composition-dependent aspect ratios. PA12HU-PTMOs exhibited higher moisture uptake than traditional thermoplastic polyurethane (TPU) due to resultant hydroxyls. Variable temperature FTIR spectroscopy demonstrated that ordered hydrogen bonding in the crystalline domains was disrupted or dissociated as the crystallites melted. Although tensile strength of segmented PA12HU-PTMOs proved lower than traditional polyurethanes due to phase-mixing, these compositions represent the first examples of film-forming, linear isocyanate-free polyurethanes with mechanical integrity and processability. [ABSTRACT FROM AUTHOR]

Addition of sulfonated terminal ligands into a Ru,Rh,Ru photocatalyst has a significant impact on the excited-state properties of the complex. The hydrophilic photocatalyst demonstrates increased solubility and H2 production in aqueous solutions. H2 production is observed under aerobic conditions for the new complex, a stark contrast to the hydrophobic analog in organic solvents. [ABSTRACT FROM AUTHOR]

ABC triblock copolymers bearing adenine- and thymine-functionalized external blocks self-assembled into long-range, ordered lamellar microphase-separated morphologies on non-patterned substrates. Intermolecular hydrogen bonding formed thymine–adenine triplets and promoted self-assembly into well-defined lamellae consisting of poly(n-butyl acrylate) soft domains and complementary nucleobase hard domains, while thymine–adenine duplets contributed to superior mechanical properties. [ABSTRACT FROM AUTHOR]

Living anionic polymerization of 4-diphenylphosphino styrene (DPPS) achieved well-defined homopolymers, poly(DPPS-b-S) styrenic block copolymers, and poly(I-b-DPPS) diene-based diblock copolymers with predictable molecular weights and narrow polydispersities. In situ FTIR spectroscopy monitored the anionic polymerization of DPPS and tracked monomer consumption for kinetic analysis. Post-alkylation enabled controlled placement of phosphonium functionality in poly(I-b-DPPS) diblock copolymers, producing well-defined phosphonium-containing block copolymers with low degrees of compositional heterogeneity. Incorporating phosphonium charge disrupted the lamellar bulk morphology of the neutral diblock precursor and provided morphologies with interdigitated packing of alkyl chains on the phosphonium cation. [ABSTRACT FROM AUTHOR]

The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H2 production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)2Ru(BL)}2RhX2]5+ (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air-saturated aqueous solution because of the quenching of the metal-to-ligand charge-transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4-styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)2Ru(dpp)}2RhCl2]5+ (bpy=2,2′-bipyridine, dpp=2,3-bis(2-pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H2 production over three times that of deoxygenated aqueous solutions alone. H2 photocatalysis proceeds even under aerobic conditions for PSS-containing solutions, an exciting consequence for solar hydrogen-production research. [ABSTRACT FROM AUTHOR]

The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H2 production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)2Ru(BL)}2RhX2]5+ (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air-saturated aqueous solution because of the quenching of the metal-to-ligand charge-transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4-styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)2Ru(dpp)}2RhCl2]5+ (bpy=2,2′-bipyridine, dpp=2,3-bis(2-pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H2 production over three times that of deoxygenated aqueous solutions alone. H2 photocatalysis proceeds even under aerobic conditions for PSS-containing solutions, an exciting consequence for solar hydrogen-production research. [ABSTRACT FROM AUTHOR]

The ability of a multiphase copolymer to exhibit both the physical properties of liquid crystalline and elastomeric polymers enables a variety of emerging applications. Traditional synthetic methods often require many steps to achieve such diversity in a copolymer. This work describes the synthesis and characterization of biphenyl-containing segmented copolyesters in a single step. A fundamental investigation of the thermal and thermomechanical properties as a function of methylene spacer length demonstrates a relationship between melting temperature and even/odd spacer lengths. DSC and SAXS analysis reveal microphase separation in these randomly segmented copolyesters. The copolymers retain a liquid crystalline morphology despite the incorporation of a flexible oligomeric polyether, and melting and isotropic temperatures ranged from 77 to 167 °C and 117 to 217 °C, respectively. Wide angle X-ray diffraction provides further insight into the effect of the soft segment on the highly crystalline nature of the segmented copolyesters. Thermomechanical analysis and tensile testing elucidate the effect of hard segment (HS) content and structure. Plateau moduli range from ≈5 to 150 MPa and increasing from 50 to 75 wt% HS doubled tensile strain. This synergy will enable superior fabrication and processing of intricate electronic devices that require high-thermal properties and mechanical durability. [ABSTRACT FROM AUTHOR]

Segmented polyurethanes based on poly(tetramethylene glycol) soft segments (SS) containing aromatic units are synthesized. Hydroquinone bis(2-hydroxyethyl) ether and 4,4′-methylenebis(phenyl isocyanate) are used as the chain extender and the diisocyanate, respectively. Effects of incorporation of hydroquinone (HQ) and triptycene hydroquinone into the soft segments on the morphology and properties of the undeformed segmented polyurethanes are investigated. Differential scanning calorimetry and dynamic mechanical analysis indicate that the incorporation of triptycene units leads to an increased glass transition temperature ( Tg) and an elimination of the crystallization of soft segments. The tensile analysis shows there is no strain hardening for the polymer films with triptycene-containing soft segments. Wide-angle x-ray diffraction demonstrates that the absence of strain hardening in triptycene-containing segmented polyurethane likely arises from the suppressed strain induced crystallization. In contrast, the less bulky HQ units show little effect on either thermally or strain induced crystallization of the soft segments. Morphology studies, including small angle x-ray scattering on the compression molded films and atomic force microscopy on the solvent cast film, reveal that polyurethanes with HQ and triptycene containing soft segments maintain distinct microphase separated morphology. [ABSTRACT FROM AUTHOR]

Reversible addition–fragmentation chain transfer (RAFT) polymerization enabled the synthesis of well-defined A–BC–A triblock copolymers containing a synergy of pendant ether and imidazolium sites. The soft central BC block comprises low Tg di(ethylene glycol) methyl ether methacrylate (DEGMEMA) and 1-(4-vinylbenzyl) methyl imidazolium units. External polystyrene blocks provide mechanical reinforcement within a nanoscale morphology. Dynamic mechanical analysis (DMA) of the A–BC–A triblock copolymers exhibited a plateau region, which suggested the formation of a microphase-separated morphology. Atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) collectively probed the morphology of the A–BC–A triblock copolymers, revealing long-range order at the nanoscale dimensions. Dielectric relaxation spectroscopy (DRS) examined the ion-transport properties of ionomeric A–BC–A triblock copolymers and random copolymers with different compositions. The role of morphology was demonstrated with block copolymer nanoscale structures providing superior ionic conductivity and mechanical performance compared to random copolymers. Under a 4 V direct current (DC) applied voltage, electromechanical transducers derived from these triblock copolymer membranes with added ionic liquid showed superior actuation performance compared to a benchmark Nafion® membrane, suggesting potential for ionic polymer device applications. This was attributed to optimum modulus, improved ionic conductivity, and microphase-separated morphology of triblock copolymers. [ABSTRACT FROM AUTHOR]

Adenine- and thymine-functionalized ammonium ionenes with variation in spacer lengths are successfully synthesized using the Michael addition post-polymerization functionalization. This report describes the influence of pendant spacer length on homoassociation and heteroassociation of complementary nucleobase-containing ionenes. The ionene homo­polymers and complementary blends with various spacer lengths show a single glass transition temperature. Higher glass transition temperatures are observed for the shorter-spacer ionene homopolymers and their blends. The hydrogen bonding interactions in both blends of adenine-containing ionenes (ionene-A) and thymine-containing ionenes (ionene-T) with both spacer lengths are studied using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). DSC analyses do not reveal hydrogen bonding interactions in the ionene blends with the shorter spacer length. In contrast, the longer spacer length ionene blends show the presence of hydrogen bonding interactions and demonstrate that homoassociation is stronger than heteroassociation. FTIR spectroscopy and AFM confirm hydrogen bonding interactions for the longer spacer ionene blends. [ABSTRACT FROM AUTHOR]

RAFT polymerization afforded acrylic ABC triblock copolymers with self-complementary nucleobase-functionalized external blocks and a low-Tg soft central block. ABC triblock copolymers self-assembled into well-defined lamellar microphase-separated morphologies for potential applications as thermoplastic elastomers. Complementary hydrogen bonding within the hard phase facilitated self-assembly and enhanced mechanical performance. [ABSTRACT FROM AUTHOR]

Elastomeric gaskets are commonly used between cells within a fuel cell stack to ensure that the reactant gases are isolated. Failure of a fuel cell gasket can cause the reactant gases to mix and can lead to failure of the fuel cell. An investigation of the durability of a hydrocarbon elastomeric seal material developed for proton exchange membrane fuel cells was performed by comparing the tearing energy required for crack propagation of as-received and environmentally aged samples. Tear force was recorded as a function of crosshead displacement rate and the critical strain energy release rate was calculated and plotted against crack growth rate. Data obtained at different temperatures were then used to generate a fracture energy master curve. Additional samples were aged in selected relevant environments and compared to the as-received material to study the effect of environmental aging on tear energy master curves. Comparison of tearing energy master curves for different test conditions showed an increase in the tearing energy for all aging environments. The tear energy master curve for testing carried out in water suggested that the crack propagation rates as low as of 10-8 ms-1 can be seen as the fracture energy approaches 80 Jm-2. [ABSTRACT FROM AUTHOR]

This report describes the synthesis and characterization of unprecedented poly(propylene glycol) ( PPG) polytrioxamide and poly(urea oxamide) ( UOx) segmented copolymers containing monodisperse hard segments. Synthesis of the segmented copolymers relied on an efficient two-step end-capping sequence, which resulted in novel difunctional oxamic hydrazide-terminated polyether oligomers. Polymerization with oxalyl chloride or 4,4′-methylenebis(cyclohexyl isocyanate) provided the desired segmented copolymers displaying thermoplastic elastomeric behavior. Variable-temperature Fourier transform infrared and 1H NMR spectroscopies confirmed the presence of hard segment structures and revealed ordered hydrogen bonding interactions with thermal dissociation profiles similar to those of polyurea and polyoxamide copolymer analogs. Dynamic mechanical analysis of PPG-UOx exhibited a longer, rubbery plateau with increased moduli compared to PPG polyurea, and tensile analysis revealed a dramatic increase in copolymer toughness due to enhanced hydrogen bonding. A new step-growth polymerization strategy is described that is capable of producing tunable hydrogen bonding segmented copolymer architectures. © 2013 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

An array of perfectly alternating polycarbonate-polydimethylsiloxane (PC-PDMS) multiblock copolymers possessing systematic variations in block molecular weights were successfully produced by coupling preformed PC and PDMS telechelic oligomers using hydrosilylation. Based on gel permeation chromatography results, the multiblock copolymers were essentially void of the oligomeric precursors. Despite the relatively large difference in solubility parameter between PC and PDMS, the multiblock copolymers exhibited significant partial miscibility between the two phases. As expected, the degree of partial miscibility was dependent on the molecular weight of the blocks with the extent of partial miscibility increasing with decreasing block molecular weights. Morphological characterization using small angle X-ray scattering showed that, at a given PC block molecular weight, the uniformity of the two phase morphology increased with increasing PDMS block molecular weight, which is consistent with a decrease in the extent of phase mixing with increasing PDMS block molecular weight. POLYM. ENG. SCI., 54:1648-1663, 2014. © 2013 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]