171 research outputs found
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Direct iminization of PEEK
Semi-crystalline poly(ether ketone)s are important high-temperature engineering thermoplastics, but are difficult to characterize at the molecular level because of their insolubility in conventional organic solvents. Here we report that polymers of this type, including PEEK, react cleanly at high temperatures with low-volatility aralkyl amines to afford stable, noncrystalline poly(ether-imine)s, which are readily soluble in solvents such as chloroform, THF and DMF and so characterizable by conventional size-exclusion chromatography
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Trifluoromethylation of carbonyl groups in aromatic poly(ether ketone)s: formation of strongly polar yet surface-hydrophobic poly(arylenenecarbinol)s
Fluoride-catalyzed reactions of trimethyl(trifluoromethyl)silane with a range of aromatic poly(ether ketone)s, both amorphous and semi-crystalline, proceed quantitatively in THF to yield soluble, amorphous polymers in which the carbon-silicon bond of CF3SiMe3 has added across the carbonyl-oxygen double bond of each carbonyl group. When the starting poly(ether ketone) is amorphous and soluble in THF the reaction is fairly rapid (hours), but is much slower (days) when the starting polymer is semi-crystalline, with only low solubility in THF. Quantitative desilylation of the resulting polymers is achieved by reaction with excess fluoride ion, affording poly(arylene-trifluoromethylcarbinol)s. These extremely polar polymers are readily soluble in protic solvents such as methanol or ethanol, to give solutions from which tough, coherent films may be cast by evaporation in air. Despite the evidently high polarity of the bulk polymers, the surfaces of cast films are relatively hydrophobic, with static water contact angles of ~ 90°. Surface analyses by XPS are consistent with enrichment of the polymer-air interface in CF3 groups
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Catechol-based macrocyclic aromatic ether-sulfones: Synthesis, characterization and ring-opening polymerization
Cyclocondensation between 4,4`-bis(4-chlorobenzenesulfonyl)biphenyl and catechol, with subsequent chromatographic separation of the reaction products, led to the isolation of four novel ether-sulfone macrocycles (cyclic dimer, -trimer, -tetramer and -pentamer). Similarly, cyclocondensation of catechol with a novel seven-ring diketone/disulfone monomer allowed the isolation of the two new aromatic ether-ketone-sulfone macrocycles, a cyclic monomer and a cyclic dimer. Transannular shielding and deshielding effects in the cyclic monomer produce substantial chemical shift differences for chemically equivalent protons in the 1H NMR spectra of the cyclic monomer and -dimer. Fluoride-initiated ring-opening polymerization of the ether-sulfone cyclic trimer affords a novel, high-molecular weight poly(ether-sulfone)
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Synthesis, x-ray structure and anion binding properties of a cryptand-like hybrid calixpyrrole
The novel cryptand in/out-3, containing two tripyrrolemethane units briged by three 1,3- diisopropylidenbenzene arms was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid state X-ray structure of the free cryptand 3 was also determined
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Conformational modulation of sequence recognition in synthetic macromolecules
The different triplet sequences in high molecular weight aromatic copolyimides comprising pyromellitimide units ("I") flanked by either ether-ketone ("K") or ether-sulfone residues ("S") show different binding strengths for pyrene-based tweezer-molecules. Such molecules bind primarily to the diimide unit through complementary π-π-stacking and hydrogen bonding. However, as shown by the magnitudes of 1H NMR complexation shifts and tweezer-polymer binding constants, the triplet "SIS" binds tweezer-molecules more strongly than "KIS" which in turn bind such molecules more strongly than "KIK". Computational models for tweezer-polymer binding, together with single-crystal X-ray analyses of tweezer-complexes with macrocyclic ether-imides, reveal that the variations in binding strength between the different triplet sequences arise from the different conformational preferences of aromatic rings at diarylketone and diarylsulfone linkages. These preferences determine whether or not chain-folding and secondary π−π-stacking occurs between the arms of the tweezermolecule and the 4,4'-biphenylene units which flank the central diimide residue
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Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement
A new, healable, supramolecular nanocomposite material has been developed and evaluated. The material comprises a blend of three components: a pyrene-functionalized polyamide, a polydiimide and pyrene- functionalized gold nanoparticles (P-AuNPs). The polymeric components interact by forming well-defined p–p stacked complexes between p-electron rich pyrenyl residues and p-electron deficient polydiimide residues. Solution studies in the mixed solvent chloroform–hexafluoroisopropanol (6 : 1, v/v) show that mixing the three components (each of which is soluble in isolation), results in the precipitation of a supramolecular, polymer nanocomposite network. The precipitate thus formed can be re-dissolved on heating, with the thermoreversible dissolution/precipitation procedure repeatable over at least 5 cycles. Robust, self-supporting composite films containing up to 15 wt% P-AuNPs could be cast from 2,2,2- trichloroethanol. Addition of as little as 1.25 wt% P-AuNPs resulted in significantly enhanced mechanical properties compared to the supramolecular blend without nanoparticles. The nanocomposites showed a linear increase in both tensile moduli and ultimate tensile strength with increasing P-AuNP content. All compositions up to 10 wt% P-AuNPs exhibited essentially quantitative healing efficiencies. Control experiments on an analogous nanocomposite material containing dodecylamine-functionalized AuNPs (5 wt%) exhibited a tensile modulus approximately half that of the corresponding nanocomposite that incorporated 5 wt% pyrene functionalized-AuNPs, clearly demonstrating the importance of the designed interactions between the gold filler and the supramolecular polymer matrix
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Synthesis and analysis of a healable, poly(propylene glycol)-based supramolecular network
An investigation into healable supramolecular networks based upon branched poly(propylene) (PPG) oligomers that feature nitroarylurea chain ends is reported. A one-pot reaction utilising bis(toluene-1,4-diisocyanate)-terminated poly(propyleneglycol) (Mn ~ 2300), a nitroarylurea recognition motif, and tris(2-aminoethyl)amine was used to synthesise several branched PPG-based oligomers. The degree of oligomerization/branching was systematically varied by changing the stoichiometry of the starting materials in this one-pot reaction. The branched oligomers thus generated self-assemble into supramolecular networks, aided by association of the nitroarylurea end groups, and from this study a material that is capable of healing at ambient temperatures was realised. The healable supramolecular material formed from these studies exhibited effective autonomous healing (80% with respect to ultimate stress) up to 6 weeks after defect formation. Furthermore, elastic recovery was observed (80% with respect to yield stress) over a period of 24 hours after the samples were elongated beyond the region of uniform strain (50%)
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Inducing hardening and healability in poly(ethylene-co-acrylic acid) via blending with complementary low molecular weight additives
The design and synthesis of low molecular weight additives based on self-assembling nitroarylurea units, and their compatibility with poly(ethylene-co-acrylic acid) copolymers are reported. The self-assembly properties of the low molecular weight additives have been demonstrated in a series of gelation studies. Upon blending at low percentage weights (≤ 5%) with poly(ethylene-co-acrylic acid) the additives were capable of increasing the stress and strain to failure when compared to the parent copolymer. By varying the percentage weight of the additive as well as the type of additive the mechanical properties of poly(ethylene-co-acrylic acid) could be tailored. Finally, the healability characteristics of the blends were improved when compared to the original polymer via the introduction of a supramolecular ‘network within a network’
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Controlled variation of monomer sequence-distribution in the synthesis of aromatic poly(ether ketone)s
The effects of varying the alkali metal cation in the high-temperature nucleophilic synthesis of a semi-crystalline, aromatic poly(ether ketone) have been systematically investigated, and striking variations in the sequence-distributions and thermal characteristics of the resulting polymers were found. Polycondensation of 4,4'-dihydroxybenzophenone with 1,3-bis(4-fluorobenzoyl)benzene in diphenylsulfone as solvent, in the presence of an alkali metal carbonate M2CO3 (M= Li, Na, K, or Rb) as base, affords a range of different polymers that vary in the distribution pattern of 2-ring and 3-ring monomer units along the chain. Lithium carbonate gives an essentially alternating and highly crystalline polymer, but the degree of sequence-randomisation increases progressively as the alkali metal series is descended, with rubidium carbonate giving a fully random and non-thermally-crystallisable polymer. Randomisation during polycondensation is shown to result from reversible cleavage of the ether linkages in the polymer by fluoride ions, and an isolated sample of alternating-sequence polymer is thus converted to a fully randomised material on heating with rubidium fluoride
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Nitroarylurea-terminated supramolecular polymers that exhibit facile thermal repair and aqueous swelling-induced sealing of defects
Bi- and tri-armed polyethylene glycol units endcapped with nitroaryl urea units have been synthesised. These endcapped polymers are able to self-assemble via complementary supramolecular interactions, specifically urea-urea and nitro-urea hydrogen bonding, to afford materials with dramatically increased mechanical and thermal properties when compared to those of the uncapped polyethylene glycol precursors. Thin films of the capped polymeric systems are able to self-repair following defect creation. Control over the mechanical and thermal characteristics (in terms of bulk viscosity) of the self-assembled networks was achieved by varying the proportion of tri-armed to bi-armed self-assembly units included in the polymer. These systems demonstrate water absorption and swelling capabilities that are also controllable by varying the ratio of the two types of unit. These physical properties have been optimised to realise a secondary pathway to puncture-repair as a result of swelling on water contact
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