Design, synthesis and computational modelling of aromatic tweezer-molecules as models for chain-folding polymer blends

Novel 'tweezer-type' complexes that exploit the interactions between pi-electron-rich pyrenyl groups and pi-electron deficient diimide units have been designed and synthesised. The component molecules leading to complex formation were accessed readily from commercially available starting materials through short and efficient syntheses. Analysis of the resulting complexes, using the visible charge-transfer band, revealed association constants that increased sequentially from 130 to 11,000 M-1 as increasing numbers of pi-pi-stacking interactions were introduced into the systems. Computational modelling was used to analyse the structures of these complexes, revealing low-energy chain-folded conformations for both components, which readily allow close, multiple pi-pi-stacking and hydrogen bonding to be achieved. In this paper, we give details of our initial studies of these complexes and outline how their behaviour could provide a basis for designing self-healing polymer blends for use in adaptive coating systems. (C) 2008 Elsevier Ltd. All rights reserved.

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 pyrenefunctionalized 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.

A novel self-healing supramolecular polymer system

Utilising supramolecular pi-pi stacking interactions to drive miscibility in two-component polymer blends offers a novel approach to producing materials with unique properties. We report in this paper the preparation of a supramolecular polymer network that exploits this principle. A low molecular weight polydiimide which contains multiple pi-electron-poor receptor sites along its backbone forms homogeneous films with a siloxane polymer that features pi-electron-rich pyrenyl end-groups. Compatibility results from a complexation process that involves chain-folding of the polydiimide to create an optimum binding site for the pi-electron-rich chain ends of the polysiloxane. These complementary pi-electron-rich and -poor receptors exhibit rapid and reversible complexation behaviour in solution, and healable characteristics in the solid state in response to temperature. A mechanism is proposed for this thermoreversible healing behaviour that involves disruption of the intermolecular pi-pi stacking cross-links as the temperature of the supramolecular film is increased. The low T-g siloxane component can then flow and as the temperature of the blend is decreased, pi-pi stacking interactions drive formation of a new network and so lead to good damage-recovery characteristics of the two-component blend.

Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of noncovalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on π-electron-rich pyrenyl residues and π-electron-deficient, chain-folding aromatic diimides that interact through complementary π–π stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

Supramolecular materials for inkjet printing: self-assembling polymer networks

Electronically complementary, low molecular weight polymers that self-assemble through tuneable π-π stacking interactions to form extended supramolecular polymer networks have been developed for inkjet printing applications and successfully deposited using three different printing techniques. Sequential overprinting of the complementary components results in supramolecular network formation through complexation of π-electron rich pyrenyl or perylenyl chain-ends in one component with π-electron deficient naphthalene diimide residues in a chain-folding polyimide. The complementary π-π stacked polymer blends generate strongly coloured materials as a result of charge-transfer absorptions in the visible spectrum, potentially negating the need for pigments or dyes in the ink formulation. Indeed, the final colour of the deposited material can be tailored by changing varying the end-groups of the π electron rich polymer component. Piezoelectric printing techniques were employed in a proof of concept study to allow characterisation of the materials deposited, and a thermal inkjet printer adapted with imaging software enabled a detailed analysis of the ink-drops as they formed, and of their physical properties. Finally, continuous inkjet printing allowed greater volumes of material to be deposited, on a variety of different substrate surfaces, and demonstrated the utility and versatility of this novel type of ink for industrial applications.

Perylene as an electron-rich moiety in healable, complementary π–π stacked, supramolecular polymer systems

A two-component, supramolecular polymer blend has been designed using a novel π-electron rich bisperylene- terminated polyether. This polymer is able to self-assemble through electronically complementary π–π stacking interactions with a π-electron-deficient chain-folding polydiimide to afford thermally healable polymer blends. Model compounds were developed to assess the suitability of the deep green complexes formed between perylene residues and chain-folding bis-diimides for use in polymer blends. The polymer blends thus synthesised were elastomeric in nature and demonstrated healable properties as demonstrated by scanning electron microscopy. Healing was observed to occur rapidly at ca. 75 degC, and excellent healing efficiencies were found by tensometric and rheometric analyses. These tuneable, stimuli-responsive, supramolecular polymer blends are compared to related healable blends featuring pyrene-terminated oligomers.

Self-assembled healable materials through a combination of pi-pi stacking and hydrogen bonding

The discovery of polymers with stimuli responsive physical properties is a rapidly expanding area of research. At the forefront of the field are self-healing polymers, which, when fractured can regain the mechanical properties of the material either autonomically, or in response to a stimulus. It has long been known that it is possible to promote healing in conventional thermoplastics by heating the fracture zone above the Tg of the polymer under pressure. This process requires reptation and subsequent re-entanglement of macromolecules across the fracture void, which serves to bridge, and ‘heal’ the crack. The timescale for this mechanism is highly dependent on the molecular weight of the polymer being studied. This process is in contrast to that required to affect healing in supramolecular polymers such as the plasticised, hydrogen bonded elastomer reported by Leibler et al. The disparity in bond energies between the non-covalent and covalent bonds within supramolecular polymers results in fractures propagating through scission of the comparatively weak supramolecular interactions, rather than through breaking the stronger, covalent bonds. Thus, during the healing process the macromolecules surrounding the fracture site only need sufficient energy to re-engage their supramolecular interactions in order to regenerate the strength of the pristine material. Herein we describe the design, synthesis and optimization of a new class of supramolecular polymer blends that harness the reversible nature of pi-pi stacking and hydrogen bonding interactions to produce self-supporting films with facile healable characteristics.

Electro-active nanofibres electrospun from blends of poly-vinyl cinnamate and a cholesteric liquid crystalline silicone polymer

Electrospinning was used to generate polymer nanofibres from blends of poly-vinyl cinnamate (PVCN) and a cholesteric silicone polymer. Only blends that contained at least 40 % of PVCN produced fibres. Both differential scanning calorimetry and electron dispersion spectroscopy data indicate that the samples are miscible over a wide temperature interval. The variation of fibre diameter with concentration is nonlinear with a well-defined minimum corresponding to an 80 % PVCN blend. The fibres are birefringent with Kerr constants similar to that of cholesteric liquid crystals. Although not significant, the Kerr constant increases with increasing silicone polymer concentration.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modem polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25-60 degrees C. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60 degrees C), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45-50 degrees C) and had lower strain hardening. Strain hardening measured at 50 degrees C gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of I defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality. (C) 2004 Elsevier B.V. All rights reserved.

The physics of baking: rheological and polymer molecular structure-function relationships in breadmaking

Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modern polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that dynamic shear plateau modulus is essentially independent of variations in MW amongst wheat varieties of varying baking performance and is not related to variations in baking performance, and that it is not the size of the soluble glutenin polymers, but the structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. The rheological properties of gas cell walls in bread doughs are considered to be important in relation to their stability and gas retention during proof and baking, in particular their extensional strain hardening properties. Large deformation rheological properties of gas cell walls were measured using biaxial extension for a number of doughs of varying breadmaking quality at constant strain rate and elevated temperatures in the range 25oC to 60oC. Strain hardening and failure strain of cell walls were both seen to decrease with temperature, with cell walls in good breadmaking doughs remaining stable and retaining their strain hardening properties to higher temperatures (60oC), whilst the cell walls of poor breadmaking doughs became unstable at lower temperatures (45oC to 50oC) and had lower strain hardening. Strain hardening measured at 50oC gave good correlations with baking volume, with the best correlations achieved between those rheological measurements and baking tests which used similar mixing conditions. As predicted by the Considere failure criterion, a strain hardening value of 1 defines a region below which gas cell walls become unstable, and discriminates well between the baking quality of a range of commercial flour blends of varying quality. This indicates that the stability of gas cell walls during baking is strongly related to their strain hardening properties, and that extensional rheological measurements can be used as predictors of baking quality.