Succinonitrile-Polymer Composite Electrolytes for Li-Ion Solid-State Batteries-The Influence of Polymer Additives on Thermomechanical and Electrochemical Properties.

A plastic crystalline electrolyte (PCE) consisting of 0.4 mol/L lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in succinonitrile (SN) was blended with poly(ethylene oxide) (PEO), poly(vinylpyrrolidone) (PVP), poly(ethylene carbonate) (PEC), and polyacrylonitrile (PAN). The influences of the regarding polymers on thermomechanical properties of the PCE were studied systematically, utilizing differential scanning calorimetry, thermogravimetric analysis, and oscillation experiments. Depending on the chosen polymer, the melting temperature and overall crystallinity of the PCE were increased. For PCEs containing PEO and PVP, overall crystallinity was enhanced the most resulting in lamellae-like superstructures, identified by light microscopy images. Furthermore, the onset for the sublimation process of SN was shifted to higher temperatures, and the mechanical strength was increased by the presence of some polymers, with exception of PEC. Electrochemical characterization, including electrochemical impedance spectroscopy and linear sweep voltammetry, revealed ionic conductivities of 10-4 S/cm at room temperature for PCE with PAN and extended electrochemical stability windows of ≥4.5 V vs lithiated graphite for PCE with PEO. By correlating the thermomechanical and electrochemical properties, some structure-property relationships were drawn, pointing out great potential for specific tailoring of PCEs by polymer additives. The synergistic effect of increasing both, mechanical stability and ionic conductivity, made the PCE + PAN composition especially attractive for a possible application in batteries.

Properties of Stereocomplex PLA for Melt Spinning.

Fibers made from biopolymers are one solution for conserving both resources and the environment. However, these fibers currently have limited strengths, which limit their use for textile applications. In this paper, a biopolymer stereocomplex poly(-lactide) (scPLA) formation on a technical scale of high-molecular-weight poly(D-lactide) (PDLA) and poly(L-lactide) (PLLA) is presented. This scPLA material is the basis for further research to develop scPLA yarns in melt spinning with technical strengths for technical application. scPLA is compared with standard and commercially available semi-crystalline PLA for the production of fibers in melt spinning (msPLA) with textile strengths. Differential scanning calorimetry (DSC) gives a degree of crystallization of 59.7% for scPLA and 47.0% for msPLA. X-ray diffraction (XRD) confirms the pure stereocomplex crystal structure for scPLA and semi-crystallinity for msPLA. scPLA and msPLA are also compared regarding their processing properties (rheology) in melt spinning. While complex viscosity of scPLA is much lower compared to msPLA, both materials show similar viscoelastic behavior. Thermal gravimetric analysis (TGA) shows the influence of the molecular weight on the thermal stability, whereas essentially the crystallinity influences the biodegradability of the PLA materials.

Synthesis and Application Studies of DOPO-Based Organophosphorous Derivatives to Modify the Thermal Behavior of Polybenzoxazine.

The DOPO-based flame-retardant additives DOPO-HQ, DOPO-AP and DOPO-Van were synthesized in varying numbers of phenolic hydroxyl groups and amine groups. Moreover, their influence on the polymerization of a bisphenol F-based benzoxazine, as well as the thermal properties of the resulting materials, were studied. All DOPO-based derivatives influenced the polymerization temperature onset with a reduction of up to 20 °C, while thermo-mechanical properties remained high. Surprisingly, phosphorous content below 0.4 wt% significantly improved the reaction against small flames yielding an increase in the limited oxygen index by 2% and a V-0 rating in the UL-94 test. DOPO-HQ proved to be the most effective additive regarding the reaction against small flames at an astonishingly low phosphorous concentration of below 0.1 wt%, whereas DOPO-AP and DOPO-Van simultaneously lowered the polymerization temperature.

Bio-Based Bisbenzoxazines with Flame Retardant Linker.

This work explores the strategy of incorporating a highly substituted reactive flame retardant into a benzoxazine moiety. For this purpose, a DOPO-based flame retardant received a chain extension via reaction with ethylene carbonate. It was then reacted with phloretic acid to obtain a diphenol end-capped molecule, and further reacted with furfurylamine and paraformaldehyde to obtain a benzoxazine monomer via a Mannich-like ring closure reaction. This four-step synthesis yielded a partly bio-based halogen-free flame retardant benzoxazine monomer (DOPO-PA-fa). The successful synthesis was proven via NMR, IR and MS analysis. The polymerization behavior was monitored by DSC and rheological analysis both showing the polymerization starts at 200 °C to yield pDOPO-PA-fa. pDOPO-PA-fa has a significant thermal stability with a residual mass of 30% at 800 °C under ambient atmosphere. Furthermore, it reached a V-0 rating against small flames and an OI of 35%. Blended with other benzoxazines, it significantly improves their thermal stability and fire resistance. It emphasizes its potential as flame retardant agent.

Carbon, Glass and Basalt Fiber Reinforced Polybenzoxazine: The Effects of Fiber Reinforcement on Mechanical, Fire, Smoke and Toxicity Properties.

Bisphenol F and aniline-based benzoxazine monomers were selected to fabricate basalt, glass and carbon fiber reinforced polybenzoxazine via vacuum infusion, respectively. The impacts of the type of fiber reinforcement on the resulting material properties of the fiber reinforced polymers (FRPs) were studied. FRPs exhibited a homogenous morphology with completely impregnated fibers and near-zero porosity. Carbon fiber reinforced polybenzoxazine showed the highest specific mechanical properties because of its low density and high modulus and strength. However, regarding the flammability, fire, smoke and toxicity properties, glass and basalt reinforced polybenzoxazine outperformed carbon fiber reinforced polybenzoxazine. This work offers a deeper understanding of how different types of fiber reinforcement affect polybenzoxazine-based FRPs and provides access to FRPs with inherently good fire, smoke and toxicity performance without the need for further flame retardant additives.

Highly Crosslinked Polybenzoxazines from Monobenzoxazines: The Effect of Meta-Substitution in the Phenol Ring.

It is possible to control the crosslink density of polymers derived from monobenzoxazines by switching the type of substituents in the phenolic ring and their relative position with respect to the phenol group. We prepared several substituted monobenzoxazines in the para and meta positions of the phenolic ring and studied how these substituents affected the polymerization temperature of monomers and the thermal stability of the final polymers and, more extensively, how they affected the crosslink network of the final polymers. Gel content and dynamic mechanical analysis confirm that ortho- and para-orienting substituents in the meta position generate highly crosslinked materials compared to para ones. This fact can lead to the design of materials with highly crosslinked networks based on monobenzoxazines, simpler and more versatile monomers than the commercial bisbenzoxazines currently in use.

Thermosetting Shape Memory Polymers and Composites Based on Polybenzoxazine Blends, Alloys and Copolymers.

When dealing with smart polymers, in particular with shape memory polymers, the polymer type and composition specify the overall material properties and in particular the extent of the shape memory effect. Polybenzoxazines as a polymer with high potential for structural applications represent a promising component for materials with both shape memory effect and structurally interesting material properties. This minireview gives insight into how the shape memory effect, in particular the shape recovery event, is influenced by internal factors such as polymer structure, morphology and external factors such as filler addition.

Effect of Babassu Natural Filler on PBAT/PHB Biodegradable Blends: An Investigation of Thermal, Mechanical, and Morphological Behavior.

Blending of biodegradable polymers in combination with low-price organic fillers has proven to be a suitable approach to produce cost-effective composites in order to address pollution issues and develop products with superior mechanical properties. In the present research work PBAT/PHB/Babassu composites with 25, 50, and 75% of each polymer and 20% of Babassu were produced by melting extrusion. Their thermal, mechanical, and morphological behavior was investigated by differential scanning calorimetry (DSC), tensile testing, and scanning electron microscopy (SEM). Blending PBAT with PHB inhibited the crystallization of both polymers whereas adding Babassu did not significantly change their melting behaviour. Incorporation of Babassu reduced the tensile strength of its respective blends between 4.8 and 32.3%, and elongation at break between 26.0 and 66.3%. PBAT as highly ductile and low crystalline polymer may be seen as a crystallization tool control for PHB as well as a plasticizer to PBAT/PHB blends and PBAT/PHB/Babassu composites. As PBAT content increases: (i) elongation at break increases and (ii) surface fracture becomes more refined indicating the presence of more energy dissipation mechanisms. As PBAT/PHB/Babassu composites are biodegradable, environmental friendly, and cost effective, products based on these compounds have a great potential since their mechanical properties such as ductility, stiffness, and tensile strength are still suitable for several applications even at lower temperatures (-40 °C).

Insight into the Mechanism of Reversible Ring-Opening of 1,3-Benzoxazine with Thiols.

The reversible ring-opening addition and fragmentation reaction of p-cresol-based N-phenylbenzoxazine with aliphatic and aromatic thiols was investigated in solvent-mediated and solvent-free reactions. Independently of the used thiol, N-phenylbenzoxazine and the thiols reacted to equilibrium with comparable amounts of reactants and products in aprotic solvent, whereas in protic solvent almost full conversions were reached. In contrast, thiol reactivity was a crucial factor in solvent-free reactions yielding fast and complete conversions for a more acidic thiol and balanced equilibrium concentrations in case of thiols with high pKa values. The strong influence of thiols with low pKa values emphasizes the relevance of the protonation step in the ring-opening reactions of 1,3-benzoxazines with thiols in absence of solvents where acidity predominates nucleophilicity. The reverse reactions, namely adduct dissociation and benzoxazine recovery, were successfully conducted at elevated temperatures and reduced pressure facilitated by the removal of the formed thiols yielding up to 95% recovered 1,3-benzoxazine. These results provide deeper understanding of the reversible ring-opening reaction mechanism of 1,3-benzoxazine with thiols.

Multifunctional Benzoxazines Feature Low Polymerization Temperature and Diverse Polymer Structures.

3,4-dihydro-3-phenyl-2H-1,3-benzoxazines derived from phenol-, resorcinol-, and phloroglucinol give monomers with one, two, and three oxazine units at a single benzene ring, respectively. Aside from the synthesis and characterization of such multifunctional benzoxazines, reactivity and polymerization behavior is studied in dependence of the oxazine functionality. Monomer reactivities are directly related to the number of oxazine functionalities present at the benzene ring yielding the lowest polymerization temperature for the trifunctional phloroglucinol-based benzoxazine. Comparing the polymerization processes and resulting structures, the trifunctional benzoxazine derivative enter new polymerization pathways, which include methylene linkages bridging aniline units, as well as the formation of carbonyl-derived structures.

Quantitative and Qualitative Analysis of Surface Modified Cellulose Utilizing TGA-MS.

With the aim to enhance interfacial adhesion of a hydrophobic polymer matrix and cellulosic fibers and fillers, chemical surface modifications with silane coupling agents are performed. Thermogravimetric analysis (TGA) could be used to determine the degree of surface functionalization. However, similar thermal properties of treated and untreated cellulose hamper a precise determination of silane loading. This contribution deals with quantitative determination of silane loading combining both TGA and elemental analysis. Firstly, silane modified celluloses were studied by FT-IR, Raman, solid state NMR spectroscopy, and polarized light microscopy in order to determine functional groups and to study the impact of chemical treatment on cellulose morphology. Secondly, thermal stability and pyrolysis processes were studied by TG-MS analysis. In order to determine the exact silane loading, the mass percentages of the appropriate elements were quantified by elemental analysis and correlated with the charred residues determined by TGA yielding a linear dependency. With that correlation, it was possible to determine silane loadings for additional samples utilizing simple TGA measurements. The main advantage of that approach is that only one calibration is necessary for routine analyses of further samples and TGA-MS coupling gives additional information on thermal stability and pyrolysis routes, simultaneously.

Peptide-polymer ligands for a tandem WW-domain, an adaptive multivalent protein-protein interaction: lessons on the thermodynamic fitness of flexible ligands.

Three polymers, poly(N-(2-hydroxypropyl)methacrylamide) (pHPMA), hyperbranched polyglycerol (hPG), and dextran were investigated as carriers for multivalent ligands targeting the adaptive tandem WW-domain of formin-binding protein (FBP21). Polymer carriers were conjugated with 3-9 copies of the proline-rich decapeptide GPPPRGPPPR-NH2 (P1). Binding of the obtained peptide-polymer conjugates to the tandem WW-domain was investigated employing isothermal titration calorimetry (ITC) to determine the binding affinity, the enthalpic and entropic contributions to free binding energy, and the stoichiometry of binding for all peptide-polymer conjugates. Binding affinities of all multivalent ligands were in the µM range, strongly amplified compared to the monovalent ligand P1 with a K D > 1 mM. In addition, concise differences were observed, pHPMA and hPG carriers showed moderate affinity and bound 2.3-2.8 peptides per protein binding site resulting in the formation of aggregates. Dextran-based conjugates displayed affinities down to 1.2 µM, forming complexes with low stoichiometry, and no precipitation. Experimental results were compared with parameters obtained from molecular dynamics simulations in order to understand the observed differences between the three carrier materials. In summary, the more rigid and condensed peptide-polymer conjugates based on the dextran scaffold seem to be superior to induce multivalent binding and to increase affinity, while the more flexible and dendritic polymers, pHPMA and hPG are suitable to induce crosslinking upon binding.

Effects of charge and charge distribution on the cellular uptake of multivalent arginine-containing peptide-polymer conjugates.

Copolymers of N-(2-hydroxypropyl)methacrylamide (HPMA) and N-methacryloyl-ß-alaninyl-S-benzyl thioester were prepared by employing free radical or RAFT conditions and denominated as "NCL polymers". The copolymer with a polydispersity index of 1.2-1.3 was used for the direct conjugation of unprotected peptides and peptide mixtures bearing differentially loaded side chains by native chemical ligation reactions conducted in aqueous buffer. Uptake into human HeLa cells was correlated with the overall surface charge and the ζ potentials of the peptide-polymer conjugates. Most notable were the differential effects found for various multivalent peptide-polymer conjugates containing arginine residues. Although positive ζ potentials were required for cellular uptake of the peptide-polymer conjugates, this sole charge effect was strongly dominated by the effect exerted by the relative distribution of arginine residues. Polymers conjugated with nona-arginine peptides were over-proportionally taken up, relative to their surface charge, compared to polymers with random distribution of single arginine residues. In view of these findings, peptide-polymer compositions suitable for efficient cellular uptake with negligible toxicity at polymer concentrations relevant for intracellular functional studies were determined.