Synthesis and thermal degradation behaviors of hyperbranched polyphosphate

A novel epoxy-terminated hyperbranched polyphosphate (E-HBPP) was synthesized by employing an A₂ + B₃ polycondensation and characterized by FTIR, ¹H NMR and GPC. E-HBPP was used as a reactive-type flame retardant for diglycidyl ether of bisphenol-A/m-phenylene diamine (DGEBA/mPDA) system. A series of flame retardant resins were prepared and their flame retardancy was monitored by the limiting oxygen index (LOI). The results showed that the LOI value of the cured samples and the degree of expansion of the formed char after burning increased along with the E-HBPP content. Their thermal degradation behaviors were investigated by thermogravimetric analysis and in situ FTIR and showed that the phosphate group of E-HBPP first degraded to form poly(phosphoric acid)s at around 300 °C, which had a major contribution to form the compact char to protect the sample from further degradation. The dynamic mechanical thermal properties were studied by dynamic mechanical thermal analysis (DMTA) and the results showed a good miscibility between E-HBPP and DGEBA. The mechanical properties of the cured films were also investigated. Less than 20% E-HBPP addition improved both the tensile strength and elongation at break.     

Synthesis of binary cyclo-tetraphosphates by thermal decomposition of polyphosphate glasses

Binary cyclo-tetraphosphates Me ₂ ^II -_xM _x ^II P₄O₁₂ were synthetized via the thermal decomposition and recrystallization of polyphosphate glasses, i.e. binary higher linear phosphates (Me ₂ ^II -_xM _x ^II )_n/4H₂P_nO_3n+l. The syntheses ofc-Zn₂-_xMg_xP₄O₁₂ andc-Zn₂-_xCa_xP₄O₁₂ are presented as examples.

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Zusammenfassung Mittels thermischer Zersetzung und Rekristallisierung von Polyphosphatgläsern, d.h. von binärem höherem, linearem Phosphat der Formel Me ₂ ^II -_xM _x ^II _n/4H₂P_nO_3n+1 wurden in unserem Laboratorium die binären Cyclotetraphosphate Me ₂ ^II M ₂ ^II P₄O₁₂ synthetisiert. Als Beispiel wird die Synthese vonc-Zn₂-_xMg_xP₄O₁₂ undc-Zn₂-_xCa_xP₄O₁₂ beschrieben.

     

Effect of zinc borate on the thermal degradation of ammonium polyphosphate

The thermal behaviour of a mixture containing an ammonium polyphosphate based compound (AP760) and zinc borate (ZB) is investigated. After an investigation of the degradation of the pure components, the interactions between them are examined by thermogravimetry. Then, X-ray diffraction (XRD) and ¹¹B and ³¹P solid-state nuclear magnetic resonance (NMR) measurements have been carried out on residues of mixtures of AP760 and FBZB heat treated at different characteristic temperatures. It reveals the nature of the interactions taking place between the two components. It is demonstrated that reactions lead to the formation of zinc phosphate and of borophosphates. Mechanisms of thermal degradation are proposed.     

Molecular determinants of protein-based coacervates

Protein–polyelectrolyte coacervates have gained interest for their potential to stabilize proteins or function as adhesives and their biological implications in the formation of membraneless organelles. To effectively design these materials or predict their biological formation, knowledge of the macromolecular properties that dictate phase separation is required. This review highlights recent advances in the understanding of molecular determinants of protein–polyelectrolyte phase behavior. Properties that promote the phase separation of protein–polyelectrolyte pairs are covered from the perspective of synthetic systems and simplified biological condensates. Prominent factors that determine coacervate formation and material properties include nonspecific intermolecular interactions, as well as specific biological interactions and structures. Here, we summarize the essential roles of electrostatics, including charge magnitude and distribution, (bio)polymer chemistry and structure, and post-translational modifications to protein phase separation in both a synthetic and cellular context.     

Synthesis,characterization, and thermal studies of cardanol-based polyphosphate esters

Polyphosphate esters were synthesized from derivatives of cardanol phosphorodichloridateates and dihydric phenols by interfacial polycondensation using a phase transfer catalyst. The polymers were characterized by IR, ¹H-, ¹³C-, and ³¹P-NMR spectroscopy, and GPC. The thermal stability and thermal degradation kinetics of the polymers were determined by thermogravimetry. The flammability of the polymers was evaluated by limiting oxygen index values. © 1993 John Wiley & Sons, Inc.     

Multistimuli responsive ternary polyampholytes: Formation and crosslinking of coacervates

A series of multiresponsive ternary polyampholytes were prepared by free‐radical copolymerization of N‐(3‐aminopropyl) methacrylamide hydrochloride (APM), methacrylic acid (MAA), and N‐(2‐hydroxyethyl) acrylamide (HEA). APM and MAA were held at 1:1 molar ratio, while the HEA monomer feed was varied between 14 and 33 mol %. Compositional drift during polymerization was monitored by ¹H nuclear magnetic resonance, and minimized by adjusting the reactivity of MAA through its degree of ionization. The resulting polyampholytes phase‐separate from aqueous solution to form coacervate droplets, depending on HEA content, pH, ionic strength, and temperature. These coacervate droplets could be covalently crosslinked and the resulting hydrogel particles were found to swell with increasing ionic strength. Such soluble and microgel polyampholytes open opportunities for new multistimuli responsive biomaterials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2109–2118     

Effect of ammonium polyphosphate on combustion and thermal degradation of aliphatic polyamides

Chain fragments with amide and imide groups are the most abundant degradation products of aliphatic polyamides (APA) which derive from scission of the N-alkylamide bond (-CH₂-NH-). In the case of polyamide 6.6 (PA-6.6), also carbodiimide structures and methyl chain ends are formed, which derive from scission of -CH₂-C(=O)- bond. Cyclic compounds can be formed besides chain fragments, depending on the type of APA. Ammonium polyphosphate (APP) reacts with APA on heating forming phosphoric esters which decompose giving products similar to those obtained from pure APA. APP increases the yield of carbodiimides from PA-6.6 which trimerise to triazine structures. The fire retardant mechanism of APP is discussed on the basis of the thermal degradation of the mixtures.     

Co-microencapsulate of ammonium polyphosphate and pentaerythritol and kinetics of its thermal degradation

Co-microencapsulated ammonium polyphosphate (APP) and pentaerythritol (PER) (M (A&P)) is prepared using melamine-formaldehyde (MF) resin by in situ polymerization method, and characterized by Energy dispersive spectrometer (EDS) and Fourier transform infrared (FTIR) spectra. Thermal stability of M (A&P) has been analyzed and compared with APP/PER mixture. In air atmosphere, the mass loss of M (A&P) at different heating rates was investigated using TGA. The kinetics of thermal degradation and activation energy was described using Flynn-Wall-Ozawa and Kissinger methods. It showed that there were two degradation stages. Expanded carbon structure with honeycomb was formed in the first stage between 200 and 450 °C. The second stage was the oxidation of carbon with E_a as high as 151.7 kJ/mol, so the expanded carbon had a good thermal stability. The reaction order of thermal degradation was found to be 0.935, so the mechanism of M (A&P) thermal degradation was controlled by the process of random nuclear formation and growth.     

Complex dynamics of multicomponent biological coacervates

Phase transitions and coacervates play key roles in natural and synthetic soft matter. In particular, the past few years have seen a rapid expansion in studies of these phenomena in the context of dynamic cellular compartmentalization. In this brief review, we mainly focus on a few concepts and selected in vitro and cellular examples of recent developments in the areas of dynamics and multicomponent systems. Topics covered include the flexibility and conformational dynamics of polymeric species involved in phase separation, valence and non-monotonic effects, noise modulation and feedback loops, and multicomponent systems and substructure. The fundamental concepts discussed in this review are widely applicable, including in the context of cellular function and the development of materials with novel properties.     

Synergistic effects of ammonium polyphosphate and red phosphorus with expandable graphite on flammability and thermal properties of HDPE/EVA blends

In this work, the flame‐retardant high‐density polyethylene/ethylene vinyl‐acetate copolymer (HDPE/EVA) composites have been prepared by using expandable graphite (EG) as a flame retardant combined with ammonium polyphosphate (APP) and red phosphorus masterbatch (RPM) as synergists. The synergistic effects of these additives on the flammability behaviors of the filled composites have been investigated by limiting oxygen index, UL‐94 test, cone calorimeter test, thermogravimetric analysis (TGA), Fourier‐transform infrared (FTIR), and scanning electron microscopy. The results show that APP and RPM are good synergists for improving the flame retardancy of EG‐filled HDPE/EVA composites. The data from TGA and FTIR spectra also indicate the synergistic effects of APP and RPM with EG considerably enhance the thermal degradation temperatures but decrease the charred residues of the HDPE/EVA/EG composites because the flame‐retardant mechanism has changed. The morphological observations present positive evidences that the synergistic effects take place in APP and RPM with EG in flame‐retardant EG‐filled HDPE/EVA/EG composites. The formation of stable and compact charred residues promoted by APP and RPM with EG acts as effective heat barriers and thermal insulations, which improves the flame‐retardant performances and prevents the underlying polymer materials from burning. Copyright © 2015 John Wiley & Sons, Ltd.     

The effect of ammonium polyphosphate on the mechanism of thermal degradation of polyureas

The thermal decomposition of structurally related N–H and N,N′-disubstituted polyureas (Table I) and their mixtures with ammonium polyphosphate (APP) was investigated by thermogravimetry (TG) and direct pyrolysis in a mass spectrometer (MS). The N–H polyureas (IV–VI) undergo a quantitative depolymerization process with the formation of oligomers with amine and isocyanate end groups. In contrast, the thermal degradation of the N,N′-disubstituted polyureas (I–III) proceeds by a different mechanism as a function of their chemical structure. The addition of APP lowers the thermal stability of the N,N′-disubstituted polyureas, whereas that of the N–H polyureas is unaltered. However, our data show that APP does not change the nature of the pyrolytic products. The destabilizing effect of the additive can be attributed to the catalytic action of the acid species formed by its thermal decomposition.     

Simple coacervates of zein to encapsulate Gitoxin

This work reports the use of simple coacervates of the hydrophobic protein zein to encapsulate Gitoxin, a cardiotonic glycoside. The microspheres obtained using ethanol, methanol, iso-propyl alcohol were characterized using viscosity index, scanning electron microscopy (SEM) and laser light scattering particle analyzer. Scanning electron micrographs indicated that the zein film was made of microspheres with diameter in the 1-1.5 microm range, which could be controlled. Sizes of Gitoxin-loaded zein microspheres changed little before and after release of the drug because of conglutination among zein microspheres. Release of Gitoxin from zein microspheres, were performed in vitro to investigate the mechanism of model drug release. The results show that the zein microspheres obtained using ethanol are best suited for use as a sustained-release form of Gitoxin. The microspheres may also be useful in drug targeting system since the diameter of the microspheres is appropriate for phagocytosis by macrophages. Both zein film and Gitoxin-loaded zein microsphere film were effective in suppressing platelet adhesion.     

Synthesis and thermal behaviour of polyamide 6/bentonite/ammonium polyphosphate composites

In order to achieve acceptable levels of flame retardancy of polymers, phosphorus-based flame retardant (FR) additives at about 20-30% w/w are required which is too high for conventional synthetic fibres. To know whether more finely sized particles of conventional FRs with or without nanoclay are more effective at the same concentration, composites of PA6 with bentonite and ammonium polyphosphate (APP) have been prepared by melt processing in a twin-screw extruder. XRD peaks and TEM images of PA6/Org-bentonite composite show partially ordered intercalation and ordered exfoliation. Thermal analysis in He shows that thermal stability of PA6 nanocomposite has increased by 18 °C compared with pure PA6 during degradation after 425 °C but it has decreased by 100 °C on inclusion of APP in PA6/nanoclay composites. The char yield is increased by 20% in PA6/bentonite/APP composites. No effect on thermal stability or char yield is observed by reducing the particle size of APP.     

Synthesis,spectral, thermal,and flammability studies of phenolphthalein polyphosphate esters

Polyphosphate esters were synthesized from phenolphthalein and aryl phosphorodichloridates by interfacial polycondensation using a phase transfer catalyst. The polymers were characterized by IR, ¹H-, ¹³C-, and ³¹P-NMR spectroscopy. The molecular weights were calculated by end group analysis using ³¹P-NMR spectral data. The thermal stability of the polymers was studied by thermogravimetry and the flammability was investigated by measuring limiting oxygen index values.     

Infrared study of the effects of thermal treatment on montmorillonite-benzidine complexes

Li-, Na-, K-, Rb- and Cs-montmorillonites were saturated with benzidine, these organo-clay complexes heated under vacuum to 200°C and IR spectra recorded at various temperatures. Benzidine is mostly bound to interlayer cations through water molecules, except in Cs-clay where bonding to hydrophobic water and to water molecules which are hydrogen bonded to the oxygen plane predominates. During the thermal treatment water is lost and alkali, cations coordinate directly with benzidine. In Cs-, and to some extent also in Rb- and K-montmorillonite, benzidine is oxidized to semiquinone and quinoidal cation during the thermal treatment.     

The effects of thermal treatment on the antioxidant activity of polyaniline

The thermal stability of chemically synthesized polyaniline (PANI) was examined, including granular (G) polyaniline powders formed conventionally in an HCl medium, and nanorod (NR) samples prepared using a falling-pH synthesis. The samples were examined before and after dedoping (dd) using thermogravimetric analysis (TGA), which showed small mass losses in the 200-300 °C temperature range, and greater mass losses due to oxidative degradation at higher temperatures. Furthermore, samples were treated thermally at 100, 125, 150, 175, 200, 250 and 300 °C for 30 min in air. SEM images did not show any pronounced effect on the morphologies of the samples from thermal treatment up to 300 °C. The ratios of the intensities (Q/B) of the predominantly quinonoid (Q) and benzenoid peaks (B) from FTIR spectroscopic analysis revealed that NR-PANI and NR-PANIdd underwent cross-linking upon thermal treatment up to 175 °C and were oxidized after treatment above 175 °C. G-PANI and G-PANIdd also underwent the same chemical changes with oxidation occurring above 200 °C. The free radical scavenging capacity of the samples was evaluated using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay, and was found to be independent of the spin concentrations of the samples. All samples exhibited a rapid decline in free radical scavenging capacity when exposed to temperatures above 200 °C, indicating that any polymer processing should be undertaken at temperatures less than this value to achieve high antioxidant activity.     

Infrared study of the effects of thermal treatment on montmorillonite-benzidine complexes

Transition metal montmorillonites were saturated with benzidine (BEN) and heated gradually to 200°C, in a vacuum cell supported by KBr windows. IR spectra were recorded before and after the thermal treatment and at various temperatures during this treatment. X-ray diffractions were recorded before and after the thermal treatment. Hg clay shows properties similar to those of Mg and Ca clays. In the interlayer BEN is bound to Hg through a water molecule bridge, either by proton accepting (typeA) or by proton donation (typeB). Some BEN is also protonated (typeD). Initially typeA predominates, but after the thermal treatment, when the film is rehydrated, the amounts of typesB andD increase. With Mn-, Co-, Ni-, Zn- and Cd-montmorillonite a direct coordination of the benzidine by the dehydrated metallic cation is obtained (typeC), in addition to small amounts of typesA,B andD. During the thermal treatment water is evolved and associationsA andB are completely transformed toC. At elevated temperatures the following associations were identified in trace amounts, ammonium-amine, BEN bound to non-structured water, hydrophobic adsorbed BEN and BEN bound to the oxygen plane (typesE, F, H andJ, respectively). During the thermal treatment of Co and Cd clays some of the benzidine was oxidized, probably to semiquinone and quinoidal cation.     

Synthesis and thermal decomposition of a novel hyperbranched polyphosphate ester used for flame retardant systems

A novel hyperbranched polyphosphate ester (HPPE) was synthesized via the polycondensation of bisphenol-A as an A₂ monomer and phosphoryl trichloride as a B₃ monomer at 100 °C, without gelation. The initial molar ratio of A₂ to B₃ was set to be 1.5:1. The final product was precipitated from methanol. ³¹P NMR spectroscopy was used to monitor the reaction. The formed HPPE was characterized by FTIR and ¹H NMR to confirm its end groups. Differential scanning calorimetry data revealed that the cured bisphenol-A epoxy resin with HPPE as a curing agent possessed improved glass transition temperature. Dynamic mechanical thermal analysis also showed the increase in the glass transition temperature. The thermal degradation properties and flame retardancy were investigated by thermogravimetric analysis and limiting oxygen index (LOI). The results showed that the incorporation of HPPE into bisphenol-A epoxy resin increased its thermal stability and char yield during the decomposition by raising the second stage decomposition temperature. The LOI value increased from 23 to 31 when HPPE, instead of bisphenol-A, was used as a curing agent.     

Conductivity and structure of a group of lipid coacervates

Some theories concerning the structure and properties of coacervates are discussed. The preparation of a type of lipid coacervate, suitable as a biological model, especially for olfactory transduction, is described. When organic substances are added, the conductivity of the coacervate decreases roughly in proportion to the amount of additive. The sensitivity to 20 different additives has been investigated. In general, the sensitivity was greater, the longer the chain of the additive. The sensitivity pattern was also dependent on the composition of the coacervate and although the dependence appeared to be very complex, some clear traits could be distinguished. Experimental studies on the optical and diffusional properties and composition of the coacervate are presented. The coacervate was found to be optically isotropic. Its total Na⁺ concentration was about the same as in the equilibrium liquid, whereas the Cl⁻ concentration in coacervate water was lower than in equilibrium liquid. Both remained fairly constant as the coacervate shrank under the influence of added toluene. The diffusion velocities of tartrazine and Sudan black B in coacervate were of the same order of magnitude, which suggests that the lipids may form a continuous network throughout the coacervate phase, rather than discrete micelles.