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Polystyrene (PS) was modified by covalently binding P-, P-N- and/or N- containing fire-retardant moieties through co- or ter-polymerization reactions of styrene with diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl-p-vinylbenzyl phosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methylamino]ethyl ester (ADEPMAE) and maleimide (MI). In the present study, the condensed-phase and the gaseous-phase activities of the abovementioned fire retardants within the prepared co- and ter-polymers were evaluated for the first time. Pyrolysis–Gas Chromatography/Mass Spectrometry was employed to identify the volatile products formed during the thermal decomposition of the modified polymers. Benzaldehyde, α-methylstyrene, acetophenone, triethyl phosphate and styrene (monomer, dimer and trimer) were detected in the gaseous phase following the thermal cracking of fire-retardant groups and through main chain scissions. In the case of PS modified with ADEPMAE, the evolution of pyrolysis gases was suppressed by possible inhibitory actions of triethyl phosphate in the gaseous phase. The reactive modification of PS by simultaneously incorporating P- (DEAMP or DEpVBP) and N- (MI) monomeric units, in the chains of ter-polymers, resulted in a predominantly condensed-phase mode of action owing to synergistic P and N interactions. The solid-state 31P NMR spectroscopy, Scanning Electron Microscopy/Energy Dispersive Spectroscopy, Inductively-Coupled Plasma/Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy of char residues, obtained from ter-polymers, confirmed the retention of the phosphorus species in their structures.

Diblock copolymers (BCP) consisting of poly(methyl methacrylate) (PMMA) and poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PsfMA) blocks are employed as templates for controlled dispersion and localization of multi-walled carbon nanotubes (MWCNT). Short MWCNT are modified with perfluoroalkyl groups to increase the compatibility between MWCNT and the semifluorinated (PsfMA) phase and to promote a defined arrangement of MWCNT in the BCP morphology. Thin BCP and BCP/MWCNT composite films are prepared by dip-coating using tetrahydrofuran as solvent with dispersed MWCNT. Atomic force microscopy, scanning and transmission electron microscopy reveal a strong tendency of the BCP to form micelle-like domains consisting of a PMMA shell and a semifluorinated PsfMA core, embedded in a soft phase, containing also semifluorinated blocks. MWCNT preferentially localized in the embedding phase outside the micelles. Perfluoroalkyl-modification leads to significant improvement in the dispersion of MWCNT, both in the polymer solution and the resulting nanocomposite film due to increased interaction of MWCNT with the semifluorinated side chains in the soft phase outside the micelle domains. As a result, reliable electrical conductivity is observed in contrast to films with non-modified MWCNT. Thus, well-dispersed, modified MWCNT provide a defined electrical conduction path at the micrometer level, which is interesting for applications in electronics and vapor sensing.

The interest in bio‐based alternatives to classical polyesters such as poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) is steadily growing to achieve a more sustainable approach to polymer materials. In this study, PBT/poly(butylene furanoate) (PBF) blends are prepared, characterized and extrusion foamed. PBF as a bio‐based polyester offers two advantages. The ecological footprint of the material is reduced, and additionally, it can be used in Diels‐Alder reactions at the blend surface to support fusion of the foamed beads. The blending behavior of the polyesters is investigated using samples prepared in a microcompounder, particularly focused on the miscibility of the blends and transesterification reactions. The blends are thermodynamically immiscible but show a certain degree of transesterification according to nuclear magnetic resonance (NMR) spectroscopy. The morphology of blend beads produced by an extrusion foaming process is analyzed regarding their cell density, cell size distribution, and open‐cell content. It is shown that PBF has a positive effect on the bead foam morphology. The use of a bifunctional linker designed for chemical fusion of the bead surfaces allows to obtaining of molded parts, in contrast to beads containing pure PBT.

Understanding the interplay between the molecular structure of the ionic liquid (IL) subunit, the resulting nanostructure and ion transport in polymerized ionic liquids (PILs) is necessary for the realization of high-performance solid-state electrolytes required in various advanced applications. Herein, we present a detailed structural characterization of a recently synthesized series of acrylate-based PIL homopolymers and networks with imidazolium cations and chloride anions with varying alkyl spacer and terminal group lengths designed for organic solid-state batteries based on X-ray scattering. The impact of the concentrations of both the crosslinker and added tetrabutylammonium chloride (TBACl) conducting salt on the structural characteristics is also investigated. The results reveal that the length of both the spacer and terminal group influence the chain packing and, in turn, the nanophase segregation of the polar domains. Long spacers and terminal groups seem to induce denser polar aggregates sandwiched between more compact alkyl spacer and terminal group domains. However, the large inter-backbone spacing achieved seems to limit the ionic conductivity of these PILs. More importantly, our findings show that the previously reported general relationships between the ionic conductivity and the structural parameters of the nanostructure of PILs are not always attainable for different molecular structures of the IL side group.

Polymeric single chloride-ion conductor networks based on acrylic imidazolium chloride ionic liquid monomers AACXImCYCl as reported previously are prepared. The chemical structure of the polymers is varied with respect to the acrylic substituents (alkyl spacer and alkyl substituent in the imidazolium ring). The networks are examined in detail with respect to the influence of the chemical structure on the resulting properties including thermal behavior, rheological behavior, swelling behavior, and ionic conductivity. The ionic conductivities increase (by two orders of magnitude from 10 −6 to 10 −4 S·cm −1 with increasing temperature), while the complex viscosities of the polymer networks decrease simultaneously. After swelling in water for 1 week the ionic conductivity reaches values of 10 −2 S·cm −1 . A clear influence of the spacer and the crosslinker content on the glass transition temperature was shown for the first time in these investigations. With increasing crosslinker content, the T g values and the viscosities of the networks increase. With increasing spacer length, the T g values decrease, but the viscosities increase with increasing temperature. The results reveal that the materials represent promising electrolytes for batteries, as proven by successful charging/discharging of a p(TEMPO-MA)/zinc battery over 350 cycles.

The effects of covalently bound phosphorus (P-) and nitrogen (N-) bearing groups on the thermal and combustion attributes of polystyrene have been investigated. The necessary chemical modifications were achieved through co - and ter- polymerisation reactions, in a suitable solvent, under radical initiation conditions. The influence of P–N cooperative interactions on the combustion properties of styrenic polymers was studied. The co -monomers of interest included: diethyl(acryloyloxymethyl)phosphonate (DEAMP), diethyl- p -vinylbenzylphosphonate (DEpVBP), acrylic acid-2-[(diethoxyphosphoryl)methyl amino]ethyl ester (ADEPMAE) and maleimide (MI). For the first time, the ter- polymers of styrene containing both P- groups, DEAMP or DEpVBP, and N- groups, MI, were prepared via solution polymerisation. It was found that the thermal stability and combustion characteristics of polystyrene were significantly altered by the presence of nominal amounts of P- and N- containing groups, and, in certain cases, cooperative interactions of these groups were also evident. For instance, the extents of char formation post-degradation of the prepared ter- polymers, as revealed by thermogravimetric investigations in an inert atmosphere (nitrogen), were found to be enhanced by more than 20%, as compared to the unmodified polystyrene. The heat release rates and heat release capacities of the ter- polymers, as measured using the pyrolysis combustion flow calorimetric (PCFC) technique, were reduced by almost 50% in comparison to the same parameters obtained for the unmodified counterpart.

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young’s modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10−6 S·cm−1 at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10−5 S·cm−1 and further increases to 10−3 S·cm−1 in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries.

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young’s modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10[sup.−6] S·cm[sup.−1] at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10[sup.−5] S·cm[sup.−1] and further increases to 10[sup.−3] S·cm[sup.−1] in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries.

The aspects of fire retardation in some phosphorus-modified polymethyl methacrylate (PMMA) and polystyrene (PSt) polymers are reported in the present paper. Both additive and reactive strategies were employed to obtain the desired level of loading of the phosphorus-bearing compound/moiety (2 wt.% of P in each case). Test samples were obtained using bulk polymerization. The modifying compounds contained the P-atom in various chemical environments, as well as in an oxidation state of either III or V. With a view to gain an understanding of the chemical constitution of the gaseous products formed from the thermal decomposition of liquid additives/reactives, these materials were subjected to GC/MS analysis, whereas the decomposition of solid additives was detailed using the pyrolysis-GC/MS technique. Other investigations included the use of: Inductively-coupled Plasma/Optical Emission Spectroscopy (ICP/OES), solid-state NMR and FT-IR spectroscopy. In the case of PMMA-based systems, it was found that the modifying phosphonate ester function, upon thermal cracking, produced ‘phosphorus’ acid species which initiated the charring process. In the case of solid additives, it is more likely that the resultant phosphorus- and/or oxygenated phosphorus-containing volatiles acted as flame inhibitors in the gaseous phase. With the PSt-based systems, a probable process involving the phosphorylation of the phenyl groups leading to crosslinking and char formation is feasible.

The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing compounds, among them a number of compounds not reported so far. These PIR foams are compared with PIR foams without FR and with standard FRs with respect to foam properties, thermal decomposition, and fire behavior. Although BPPO and DOPO differ by just one oxygen atom, the impact on the FR properties is very significant: when the FR is a filler or a dangling (dead) end in the PIR polymer network, DOPO is more effective than BPPO. When the FR is a subunit of a diol and it is fully incorporated in the PIR network, BPPO delivers superior results.