Structure and Properties of Metallosupramolecular Polymers with a Nitrogen-Based Bidentate Ligand.

The solid-state properties of supramolecular polymers that feature metal-ligand (ML) complexes are, in addition to the general nature of the monomer, significantly affected by the choice of ligand and metal salt. Indeed, the variation of these components can be used to alter the structural, thermal, mechanical, and viscoelastic properties over a wide ranges. Moreover, the dynamic nature of certain ML complexes can render the resulting metallosupramolecular polymers (MSPs) stimuli-responsive, enabling functions such as healing, reversible adhesion, and mechanotransduction. We here report MSPs based on the bidentate ligand 6-(1'-methylbenzimidazolyl) pyridine (MBP), which is easily accessible and forms threefold coordination complexes with various transition metal ions. Thus, a poly(ethylene-co-butylene) telechelic was end-functionalized with two MBP ligands and the resulting macromonomer was assembled with the triflate salts of either Zn2+, Fe2+, or Ni2+. All three MSPs microphase separate and adopt, depending on the metal ion and thermal history, lamellar or hexagonal morphologies with crystalline domains formed by the ML complexes. The melting transitions are well below 200 °C, and this permits facile (re)processing. Furthermore, defects can be readily and fully healed upon exposure to UV-light. While the three MSPs display similar moduli in the rubbery regime, their extensibility and tensile strength depend on the nature of the ML complex, which similarly affects the long-range order and dynamic behavior.

Plasticization of a Semicrystalline Metallosupramolecular Polymer Network.

The assembly of ligand-functionalized (macro)monomers with suitable metal ions affords metallosupramolecular polymers (MSPs). On account of the reversible and dynamic nature of the metal-ligand complexes, these materials can be temporarily (dis-)assembled upon exposure to a suitable stimulus, and this effect can be exploited to heal damaged samples, to facilitate processing and recycling, or to enable reversible adhesion. We here report on the plasticization of a semicrystalline, stimuli-responsive MSP network that was assembled by combining a low-molecular-weight building block carrying three 2,6-bis(1'-methylbenzimidazolyl) pyridine (Mebip) ligands and zinc bis(trifluoromethylsulfonyl)imide (Zn(NTf2)2). The pristine material exhibits high melting (T m = 230 °C) and glass transition (T g ≈ 157 °C) temperatures and offers robust mechanical properties between these temperatures. We show that this regime can be substantially extended through plasticization. To achieve this, the MSP network was blended with diisodecyl phthalate. The weight fraction of this plasticizer was systematically varied, and the thermal and mechanical properties of the resulting materials were investigated. We show that the T g can be lowered by more than 60 °C and the toughness above the T g is considerably increased.

Mechanical Behavior of Thermoplastic Starch: Rationale for the Temperature-Relative Humidity Equivalence.

This paper aimed at understanding and rationalizing the influence of both temperature and relative humidity on the mechanical behavior of thermoplastic starch (TPS). DMA experiments revealed that water molecules impact the crosslinking network by reducing the intermolecular hydrogen bond density, resulting in a less dense entanglement network. In addition, the in-situ X-ray characterization during hydration of starch revealed structural changes, which were ascribed to conformational changes in the starch chain, due to their interaction with the uptake water molecules. Finally, the study of TPS uniaxially stretched at different temperatures and humidity showed that the mechanical behavior of TPS could be rationalized by considering the ΔT parameter, which corresponds to the temperature difference between the drawing temperature and the glass transition temperature of TPS.

Lactide Lactone Chain Shuttling Copolymerization Mediated by an Aminobisphenolate Supported Aluminum Complex and Al(OiPr)3: Access to New Polylactide Based Block Copolymers.

The chain shuttling ring-opening copolymerization of l-lactide with ε-caprolactone has been achieved using two aluminum catalysts presenting different selectivities and benzyl alcohol as chain transfer agent. A newly synthesized aminobisphenolate supported aluminum complex affords the synthesis of lactone rich poly(l-lactide-co-lactone) statistical copolymeric blocks, while Al(OiPr)3 produces semicrystalline poly(l-lactide) rich blocks. Transalkoxylation is shown to operate efficiently. The crystalline ratios and glass transition temperatures of these new classes of polylactide based block copolymers can be tuned by adjusting the catalysts and the comonomers ratio.

A one pot one step combined radical and ring-opening route for the dual functionalization of starch in aqueous medium.

Starch based materials are attractive bio-based alternative to fully synthetic polymers. Native starch has however limited thermoprocessability and properties and must be modified. In order to improve the properties of starch-graft-poly(butyl-acrylate-co-styrene) copolymers via a process as green as possible, we report herein a new method for the dual functionalization of the polysaccharide via a one pot one step reaction in aqueous medium combining free radical polymerizations and ring-opening chemistry. Poly(butyl acrylate) or poly(butyl acrylate-co-styrene) (ca. 60 000 g/mol) and oligo(ε-caprolactone) were grafted on starch with a grafting percentage up to 75 %. The copolymers show two glass transition temperatures: one around 55-60 °C related to starch and a second attributed to the grafted vinyl polymers, from -46 °C to 20 °C depending on butyl acrylate/styrene ratio. The resulting dual functionalized materials exhibit excellent mechanical properties, with elongation at break in the range 20-210 %, while single functionalized starch shows less than 5 %.

Influence of polymerization pressure and post-cure treatment on conversion degree and viscoelastic properties of polymer infiltrated ceramic network.

This study aimed at determining an optimum polymerization pressure for Polymer Infiltrated Ceramic Network (PICN) blocks by characterizing the conversion degree (DC) and the viscoelastic properties of experimental PICN blocks polymerized at 90 °C under various high pressures followed or not by post-cure treatment (PC). Near infrared analysis and dynamic mechanical analysis were used to characterize DC and viscoelastic properties of sixteen PICN: one control (thermo-cured) and fifteen experimental groups (one thermo-cured followed by PC and fourteen high pressure polymerized PICN, in the range of 50-350 MPa without and with PC). Conversion degree of high pressure polymerized PICN blocks without post curing displays an optimum between 100 and 150 MPa resulting in an improved E' and Tg. Post curing induces a higher DC with a controversial effect on thermomechanical properties. The results suggested that 100-150 MPa without PC is an optimum polymerization parameter, resulting in PICN blocks with significantly better DC, Tg, E'.

Organocatalytic sequential ring-opening polymerization of a cyclic ester and anionic polymerization of a vinyl monomer.

Organocatalysis has provided new tools for making block copolymers, in particular active species able to polymerize monomers of different chemical nature such as cyclic esters, cyclic carbonates and epoxides. We report herein the first example of an organocatalytic active species able to polymerize sequentially a cyclic ester, ε-decalactone, and a vinyl monomer, methyl methacrylate. The resulting block copolymer shows the properties of thermoplastic elastomers.

Impact of Nanoconfinement on Polylactide Crystallization and Gas Barrier Properties.

The barrier properties of poly(l-lactide) (PLLA) were investigated in multinanolayer systems, probing the effect of confinement, the compatibility between the confining and the confined polymer, crystal orientation, and amorphous phase properties. The multilayer coextrusion process was used to confine PLLA between two amorphous polymers (polystyrene, PS; and polycarbonate, PC), which have different chemical affinities with PLLA. Confined PLLA layers of approximately 20 nm thickness were obtained. The multinanolayer materials were annealed at different temperatures to obtain PLLA crystallites with distinct polymorphs. PLLA annealed in PC/PLLA films at 120 °C afforded a crystallinity degree up to 65%, and PLLA annealed in PC/PLLA or PS/PLLA films at 85 °C had a crystallinity degree of 45%. WAXS measurements evidenced that the PLLA lamellas between PS layers had a mixed in-plane and on-edge orientation. PLLA lamellas between PC layers were uniquely oriented in-plane. DMA results evidenced a shift of the PC glass transition toward lower temperature, suggesting the possible presence of an interphase. The development of the rigid amorphous fraction (RAF) in the amorphous phase during annealing was impacted by the confiner polymer. The RAF content of semicrystalline PLLA was about 15% in PC/PLLA, whereas it was neglectable in PS/PLLA. The oxygen barrier properties appeared to be governed by RAF content, and no impact of the PLLA polymorph or the crystalline orientation was observed. This study shows that the confinement of PLLA on itself does not impact barrier properties but that the proper choice of the confiner polymer can lead to decrease the phase coupling which creates the RAF. It is the prevention of RAF that decreases permeability.

Uranyl Cation Incorporation in the [P8W48O184]40- Macrocycle Phosphopolytungstate.

Association of uranyl nitrate with the macrocycle [P8W48O184]40- in formate buffered aqueous solution leads to the formation of a new compound (K11.3Li8.1Na22)[(UO2)7.2(HCOO)7.8(P8W48O184)Cl8]·89H2O (1). Its characterization by XRD reveals a high disorder of the uranyl cations and the formation of monodimensional chains of anionic [(UO2)7.2(HCOO)7.8(P8W48O184)Cl8]41.4- entities linked through formate ligands. The uranyl species are located either in the coordinating sites of the macrocycle [P8W48O184]40- or at its surface. Further studies of the molecule by SAXS and TEM show that the 1D chain collapses to give rise to the formation of polydisperse spherically aggregated species with an average radius of 129 Å.

Formation of a new type of uranium(iv) poly-oxo cluster {U38} based on a controlled release of water via esterification reaction.

A new strategy for the synthesis of large poly-oxo clusters bearing 38 tetravalent uranium atoms {U38} has been developed by controlling the water release from the esterification reaction between a carboxylic acid and an alcohol. The molecular entity [U38O56Cl40(H2O)2(ipa)20]·(ipa) x (ipa = isopropanol) was crystallized from the solvothermal reaction of a mixture of UCl4 and benzoic acid in isopropanol at temperature ranging from 70 to 130 °C. Its crystal structure reveals the molecular assembly of the UO2 fluorite-like inner core {U14} with oxo groups bridging the uranium centers. The {U14} core is further surrounded by six tetrameric sub-units of {U4} to form the {U38} cluster. Its surface is decorated by either bridging- and terminal chloride anions or terminal isopropanol molecules. Another synthesis using the same reactant mixture at room temperature resulted in the crystallization of a discrete dinuclear complex [U2Cl4(bz)4(ipa)4]·(ipa)0.5 (bz = benzoate), in which each uranium center is coordinated by two chlorine atoms, four oxygen atoms from carboxylate groups and two additional oxygen atoms from isopropanol. The slow production of water released from the esterification of isopropanol allows the formation of the giant cluster with oxo bridges linking the uranium atoms at a temperature above 70 °C, whereas no such oxo groups are present in the dinuclear complex formed at room temperature. The kinetics of {U38} crystallization as well as the ester formation are analyzed and discussed. SAXS experiments indicate that the {U38} species are not dominant in the supernatant, but hexanuclear entities which are closely related to the [U6O8] type are formed.

Processing of PVDF-based electroactive/ferroelectric films: importance of PMMA and cooling rate from the melt state on the crystallization of PVDF beta-crystals.

Poly(vinylidene difluoride) (PVDF) displays attractive ferroelectric/piezoelectric properties and its polar ß-crystals are specifically targeted for achieving electroactive applications. However, their direct crystallization from the melt state represents a challenging task that has never been addressed using melt-state processes. The use of poly(methyl methacrylate) (PMMA) is herein investigated to promote the PVDF polar ß-phase using melt-blending and extrusion-calendering technologies. The presence of the ß-phase is here confirmed by ATR-FTIR and WAXS experiments with blends at a PMMA content as low as 5 wt%. The key role of PMMA for the ß-phase crystallization from the melt state was unambiguously highlighted with the help of Flash DSC experiments in non-isothermal cooling mode from the melt state. PMMA is able to efficiently shift the α-to-ß crystal transition to lower cooling rates (>100-200 °C s-1), making the achievement of the PVDF polar ß-phase for these blends compatible with conventional processing tools. A crystal phase diagram is proposed for the PVDF/PMMA blends to highlight the dual effects of both PMMA and cooling rate on the PVDF crystallization during melt-processing. Ferroelectric properties were even observed for the blends containing PMMA up to 10 wt% with the highest remanent polarization obtained at 5 wt% PMMA. After 10 wt% PMMA, a progressive transition from ferroelectric to pseudo-linear dielectric behavior is observed more likely due to the presence of PMMA in the interlamellar amorphous phase of the polar PVDF spherulites as shown by SAXS experiments. In this work, we successfully demonstrated that PMMA plays a key role in the crystallization of PVDF polar crystals from the melt state, enabling large-scale and continuous extrusion processing of PVDF-based materials with attractive dielectric properties for sensing and harvesting applications.

Influence of fatty chain length and starch composition on structure and properties of fully substituted fatty acid starch esters.

A series of almost fully substituted Fatty Acid Starch Esters (FASEs) has been obtained in a homogeneous LiCl/DMAc medium by grafting octanoyl (C8), lauroyl (C12) and palmitoyl (C16) chlorides onto 3 starch species: Amylo-Maize, Potato and Waxy Maize. Structure-property relationships of FASEs are investigated as a function of both fatty acid chain length and amylose/amylopectin ratio of the starch. The structural study has revealed a layered type organization in which starch chain planes are separated by fatty chains. The latter are interpenetrated and/or tilted for FASE-C16 whatever the origin of the starch is, and fatty chains partially crystallizes into a structure with hexagonal symmetry. FASEs with C8 and C12 side chains are totally amorphous. The mechanical behavior of FASEs is shown to depend on both side chain length and amylose/amylopectin ratio, and an increase in material ductility is observed at increasing amylose content for C8 and C12 side chains.

Optimum pressure for the high-pressure polymerization of urethane dimethacrylate.

OBJECTIVES: The aim of this study, part of our research to improve properties of resin composite blocks suitable for CAD/CAM and to better understand underlying mechanisms associated with high-temperature/high-pressure (HT/HP) polymerization, was to determine an optimum polymerization pressure of urethane dimethacrylate (UDMA) in the presence of an initiator (0.5% benzoyl peroxide) by determining the degree of conversion (DC) and viscoelastic properties of polymers obtained at 90°C under varying HP. METHODS: DC and viscoelastic properties of 16 UDMA polymers, two controls (thermo-cured and thermo-cured followed by post-cure relaxation) and 14 experimental groups (HP polymers, in the range of 50-350 MPa, in 50 MPa increments, without and with post-cure relaxation) were determined via near infrared spectroscopic analysis and dynamic mechanical analysis, respectively. RESULTS: The results have shown that HP UDMA polymers have DC superior to that of the control group. With regards to E' and E″, the results have shown no significant difference between control and HP polymers. The damping factor, tanδ, decreased with increasing pressure, while E'rub and Tg increased. Polymerization at 150 MPa or higher resulted in significantly higher E'rub and Tg. SIGNIFICANCE: The results of this study suggested that HP polymerization at 90°C of UDMA reduced the number of defects and the free volume, leading to a more homogeneous polymer network. The results have also suggested that 200 MPa is an optimum polymerization pressure, resulting in polymers with significantly higher DC, E'rub, and Tg, while maintaining adequate damping capacity (tanδ).

Dynamic mechanical analysis of high pressure polymerized urethane dimethacrylate.

OBJECTIVES: The aim of this study was to compare the viscoelastic properties of high pressure (HP) polymerized urethane dimethacrylate (UDMA) with those of control, ambient pressure thermo-polymerized and photo-polymerized, UDMA and to assess the effect of varying polymerization parameters (protocol, temperature, and initiator) on the viscoelastic properties of HP polymerized UDMA. METHODS: The viscoelastic properties of the two control polymers, polymerized under atmospheric pressure, and four experimental polymers, polymerized under HP, were determined via dynamic mechanical analysis (DMA), in three point bending configuration. Atomic force microscopy (AFM) was used to characterize fractured polymer surface morphologies. RESULTS: The results showed that: HP-polymerization lead to a polymer with significantly higher Tg and E'rub, indicative of a higher crosslink density; modifying the polymerization protocol resulted in a significant increase in tanδ; increasing the polymerization temperature lead to a significant decrease in E'rub and Tg; and that the polymer with no initiator had the lowest E', E″, Tg, and E'rub and the highest tanδ, suggesting that under this conditions a polymer with significantly reduced crosslink density had been obtained. A characteristic nodular appearance was seen for the two control polymers under AFM, while a modified surface morphology was present in the case of HP polymerized materials. SIGNIFICANCE: The DMA results suggest that polymerization under HP resulted in polymers with an increased crosslink density and that the higher polymerization temperature or the lack of initiator was detrimental to the viscoelastic properties determined. Changes in polymer network morphology were identified by AFM characterization.

Isoprene-styrene chain shuttling copolymerization mediated by a lanthanide half-sandwich complex and a lanthanidocene: straightforward access to a new type of thermoplastic elastomers.

A lanthanide half-sandwich complex and a ansa lanthanidocene have been assessed for isoprene-styrene chain shuttling copolymerization with n-butylethylmagnesium (BEM). In the presence of 1 equiv BEM, a fully amorphous multiblock microstructure of soft and hard segments is achieved. The microstructure consists of poly(isoprene-co-styrene) blocks, with hard blocks rich in styrene and soft blocks rich in isoprene. The composition of the blocks and the resulting glass transition temperatures (Tg ) can be easily modified by changing the feed and/or the relative amount of the catalysts, highlighting a new class of thermoplastic elastomers (TPEs) with tunable transition temperatures. The materials self-organize into nanostructures in the solid state.

Water barrier properties in biaxially drawn poly(lactic acid) films.

Crystallization is among the easiest ways to improve polymer barrier properties because of the tortuosity increase within the material and the strong coupling between amorphous and crystalline phases. In this work, poly(lactic acid) (PLA) films have undergone α' thermal crystallization or different drawing processes. Although no effect of α' thermal crystallization on water permeability is observed, the drawing processes lead to an enhancement of the PLA barrier properties. This work clearly shows that, in the case of PLA, the crystallinity degree is not the main parameter governing the barrier properties contrary to the crystalline and amorphous phase organizations which play a key role. X-ray analyses confirm that the macromolecular chain orientation in the amorphous phase is the main cause of the improvement of the drawn PLA water barrier property. This improvement is due to the orthotropic structure formation for sufficient draw ratios, particularly when using the Simultaneous Biaxial drawing mode. Moreover, independently of the draw conditions, the drawing process tends to reduce the plasticization coefficient. Consequently, the drawn material barrier properties are not much affected by the water passage.