Thermal behaviour of rigid polyurethane foams

By means of a combined thermal analysis technique, the thermal behaviour of rigid polyurethane foams containing additive antipyrenes was studied. The presence of phosphorus- and phosphorus/chlorine-containing antipyrenes based on phosphate and phosphonate and a combination of them led to decreases in the rates of heat and weight loss during heating. More steps of decomposition were formed and the interval of decomposition was widened and shifted to higher temperatures. Some thermal characteristics make it possible to predict the optimum antipyrene compositions and concentrations with minimum time, labour and material consumption under laboratory conditions.

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Zusammenfassung Mittels einer kombinierten Technik wurde das thermische Verhalten eines starren, Antipyrene als Additiv enthaltenden Polyurethanschaumes untersucht. Phosphor und Phosphor/Chlor enthaltende Antipyrene auf Phosphat- und Phosphonatbasis und eine Kombination dieser Substanzen vermindern die Geschwindigkeit der Wärmeentwicklung und des Gewichtsverlustes während des Aufheizvorganges. Es treten mehr Zersetzungsschritte auf und das Temperaturintervall der Zersetzung ist größer und nach höheren Temperaturen hin verschoben. Einige thermische Kennwerte ermöglichen die Voraussage der optimalen Zusammensetzung und Konzentration des Antipyren-Additivs für minimalen Zeit-, Arbeits- und Materialaufwand unter Laboratoriumsbedingungen.

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[(4,4‐Dimethyl‐2‐oxo‐1,3‐oxazolidin‐3‐yl)methyl]phosphonic acid

The title compound, C₆H₁₂NO₅P, was synthesized as an inter­mediate phase in a search for new N‐(phosphono­methyl)glycine derivatives. The mol­ecules are held together by O—H⋯O hydrogen bonds, forming chains along the b axis in the crystal structure. The observed mol­ecular structure is compared with that calculated by the density functional theory method.     

Synthesis,NMR‐Spectroscopy,and Molecular Structure of a Phosphonyl Ene Diamine

First examples of ene diamines with a phosphonate function at the C=C double bond were obtained by the reaction of dialkyl H‐phosphonates with bis(N‐tert‐butyl)‐diimine derived from glyoxal, [1,4‐bis(tert‐butyl)‐1,4‐diaza‐1,3‐butadiene], and isolated as hydrochlorides. Preferentially the cis‐diamine is formed. The new phosphonates are characterized by multinuclear NMR spectroscopy(¹H, ¹³C, ³¹P). In addition the methyl ester 8a was characterized by ^14,15N NMR spectroscopy as well as by several 2D NMR techniques and single‐crystal X‐ray diffraction, unequivocally establishing the ene diamine structure. In the crystal dimers of the cations are formed by P–O ··· H–N hydrogen bonding.     

Introduction of phosphorus into the polyethyleneterephthalate molecule—II. A study of the influence of the modifier on the properties of polyethyleneterephthalate

The influence of the sodium salt of diethylphosphite, introduced as modifier, on the properties of polyethyleneterephthalate molecule is examined. It is shown that the detrimental effect of the salt on the normal progress of the reaction can be reduced if it is introduced at a later stage of the process. The phosphorus-containing polyethyleneterephthalate so obtained exhibits significantly improved resistance to combustion.     

Synthesis and characterization of novel (9H‐fluoren‐9‐ylamino) carbonylaminomethylphosphonic acid

The new α‐aminophosphonic acids are synthesized, reacting (9H‐fluoren‐9‐yl)urea with formaldehyde and phosphorus trichloride. (9H‐Fluoren‐9‐yl)urea was prepared from spiro(fluoren‐9,4′‐imidazolidine)‐2′,5′‐dione by alkaline hydrolysis with Ba(OH)₂. The structure of the title compounds was proved by means of IR, ¹H, ¹³C, and ³¹P NMR spectroscopy. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:719–722, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20500     

Synthesis of novel aminophosphonic acids with hydantoin structure

The novel α‐aminophosphonic acids with hydantoin structure have been synthesized reacting 5,5‐dimetylhydantoin with formaldehyde and phosphorus trichloride, or via Kabachnik–Fields reaction. Their structures were proved by means of IR, ¹H, ¹³C{¹H}, and ³¹P NMR spectroscopy. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:87–90, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20515     

Polyester-based Copolymers for Biomaterials Fabrication

Summary: Results on synthesis of poly(3-hydroxybutyrate)s possessing one or two hydroxyl groups at one terminus of the chain and carboxylic group at the other chain end are reported. These polymers were further functionalised via transesterification with dimethyl H-phosphonate thus incorporating a reactive/biodegradable center in the polyester backbone. Block/star-like copolymers composed of hydrophilic PEG and hydrophobic poly(3-hydroxybutyrate) segments linked by phosphoester moiety were also obtained. Chemical structure and composition of the reaction products were analysed applying different spectroscopic techniques (¹H, and ³¹P NMR, IR and ESI-MS) and size exclusion chromatography was applied to describe molecular weight averages and distribution.     

Synthesis of N,N-diethanolaminoethyl(methylor chloroethyl) phosphites and polyurethane elastomers from them

Transesterification of dimethyl- or bis(2-chloroethyl) phosphites with triethanolamine yields bifunctional monomers. Phosphorus- and phosphorus and chlorine-containing polyurethanes are prepared, employing N,N-diethanolaminoethyl phosphite or N,N-diethanolaminoethylchloroethyl phosphite as modifiers.     

A Study of the Reaction of Phosphorus Trichloride with Paraformaldehyde in the Presence of Carboxylic Acids

Abstract

We investigated the mechanism of the reaction of paraformaldehyde with phosphorus trichloride in the presence of carboxylic acids (acetic, propanoic, and formic). Our results revealed that bisphosphonic acids were obtained without the use of water. The structures of the reaction products were studied by 1D and 2D homonuclear and heteronuclear ¹H-, ¹³C-, ³¹P- NMR spectroscopy.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional tables.]     

Synthesis of poly(oxyethylene phosphoramidate)s and glycopolymers via Staudinger reaction: Multivalent binding studies with Concanavalin A

A new method for the preparation of poly(oxyethylene phosphoramidate)s and glycopolymers is developed via modification of poly(oxyethylene H‐phosphonate) which is a biodegradable, biocompatible and low toxic polymer. The phosphonate groups of the precursor are converted into tri‐coordinated phosphorus species yielding poly(oxyethylene trimethylsilyl phosphite). The latter is then reacted with different azides, including sugar azides, via Staudinger reaction to furnish the desired poly(oxyethylene phosphoramidate)s and such containing sugar moieties in the side chains attached to the P‐centers. 2002P NMR spectroscopy is applied as a powerful tool for determination of the conversion and structure of the reaction products. Studies on Concanavalin A binding to the obtained glycopolymers are performed using dynamic light scattering and analytical ultracentrifugation techniques. The viability of Human Embryonic Kidney 293 cell line is slightly affected when exposed to polyphosphoramidate glucoconjugate over a broad range of concentrations. The results obtained are encouraging for further investigations on the clustering and bio‐recognition properties of the synthesized glycopolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1730–1741