G. Borissov

Phosphorus-containing polyurethanes, prepared by N-modification

Abstract Phosphorus-containing polyurethanes have been prepared by N-modification by a two-step process. First the polymer is metalated by sodium hydride, and then the prepared urethane polyanion is treated with diethyl 3-bromopropylphosphonate. The structures of the modified polyurethanes have been confirmed by i.r. and 1 H-NMR. The polymers have been characterized by phosphorus content, softening temperature, solubility and reduced viscosity. It has been shown that some of the properties of the modified products depend on the degree of N-substitution. The phosphorus-containing polyurethanes possess relatively better thermal stability and enhanced fire resistance (oxygen index), which depend on the degree of substitution and the phosphorus content, respectively.

Phosphorus-containing polybenzimidazoles prepared by reaction of bis(p-carboxyphenoxymethyl)methylphosphine oxide with aromatic tetramines

Abstract Two types of polybenzimidazoles (phosphorus- and phosphorus and chlorine containing) are synthesized from bis(p-carboxyphenoxymethyl)methylphosphine oxide or its chlorine-containing analogue and aromatic tetramines in polyphosphoric acid. The structures of the new polybenzimidazoles are determined with the aid of model compounds and i.r. and u.v. spectroscopy. The polymers possess comparatively high thermal stability and resistance to ignition.

Phosphorus containing rigid polyurethane foams

Abstract Rigid polyurethane foams have been synthesized on the basis of industrial raw materials and by use of phosphorus-containing flame retardants, obtained as a result of the interaction between dialkyl phosphites and amino alcohols. The rigid polyurethane foams thus obtained are described and their thermomechanical properties and fire resistance are studied. For a low concentration of phosphorus-containing flame retardant, the rigid polyurethane foams have high fire resistance and retain their physical properties satisfactorily.

Furfuryl-containing tertiary phosphine oxides and polymers based on some of them

Abstract The syntheses of dimethyl(furfuryloxymethyl)phosphine oxide (DPO), methylbis(furfuryloxymethyl)phosphine oxide (MPO), tris(furfuryloxymethyl)phosphine oxide (TPO), dimethyl(tetrahydrofurfuryloxymethyl)phosphine oxide (DTPO), methyl-bis(tetrahydrofurfuryloxymethyl)phosphine oxide (MTPO) and tris(tetrahydrofurfuryloxymethyl)phosphine oxide (TTPO) from dimethyl(chloromethyl)phosphine oxide, methyl-bis(chloromethyl)phosphine oxide, tris(chloromethyl)phosphine oxide and the furfuryl and tetrahydrofurfuryl sodium alkoxides via the Williamson reaction are reported. Phosphorus-containing furan polymers with reduced flammability are prepared by polymerizing MPO and TPO using p -toluenesulphonic acid as catalyst. The oxygen indexes of these polymers, as determined by ASTM D-2863, are 35.1 and 33.1% O 2 , respectively; for the phosphorus-free polymer from difurfurylidene acetone, it is 23.0% O 2 . It is shown that DPO can be used as an efficient fire-retardant for reducing the flammability of a polymer from difurfurylidenacetone.

Rigid polyurethane foams with reduced flammability, modified with phosphorus- and nitrogen-containing polyol, obtained from tetrakis(hydroxymethyl)phosphonium chloride

A phosphorus- and nitrogen-containing polyol has been synthesized by condensation of tetrakis(hydroxymethyl)phosphonium chloride with diethanolamine. The newly synthesized polyol-tris[N,N-bis-(2-hydroxyethyl)aminomethyl] phosphine oxide (TPO) has been used in the preparation of rigid polyurethane foams with reduced flammability. Some of the characteristic properties of the polyurethane foams are examined. The effects of the structure and the content of the phosphorus- and nitrogen-containing polyol on properties of the polyurethanes, especially resistance to combustion, have been investigated. The influence of TPO on these properties has been compared with those of similar phosphorus- and nitrogen-containing polyols with lower functionality. Difference in the behaviour of the modified polyurethane foams has been observed, and related to the different functionalities of the phosphorus- and nitrogen-containing polyols, and to the crosslinking density of the polymers. The relationship between the oxygen index of the polyurethane foams (ΔOI) and their phorphorus content (Cp) is expressed thus: ΔOI=A+B·ln(1+Cp) It has been demonstrated that the new phosphorus- and nitrogen-containing polyol is an efficient flame retardant for rigid polyurethane foams.

Synthesis of phosphorus-containing polyurethanes from oligoethers prepared from bis(chloromethyl) methylphosphine oxide and glycols

Abstract Oligoethers with hydroxyl end-groups were prepared in boiling toluene from bis(chloromethyl)methylphosphine oxide and glycols used as monosodium glycolates. From these oligoethers and diisocyanates (hexamethylenediisocyanate and 2,4-toluene-diisocyanate), phosphorus-containing polyurethanes were synthesized.

Synthesis of polyurethanes from phosphorus-and nitrogen-containing diols obtained on the basis of tetrakis(hydroxymethyl)phosphonium chloride

Abstract Phosphorus- and nitrogen-containing diols have been prepared by condensing tetrakis-(hydroxymethyl)phosphonium chloride with secondary cyclic amines such as morpholine and pyperidine. The newly prepared diols were characterized by elemental analysis, hydroxyl values, i.r. and pmr spectroscopy. Linear polyurethanes have been prepared from phosphorus- and nitrogen-containing diols viz bis (hydroxymethyl)- N -morpholinomethylphosphine oxide or bis(hydroxymethyl)- N -pi-peridinomethylphosphine oxide and 4,4′-diphenylmethanediisocyanate; when ethylene glycol is present, copolyurethanes with different phosphorus content are also obtained. The homo- and copolyurethanes have been examined, special attention being paid to the thermogravimetric analysis data and their combustibility (oxygen index).

Rigid polyurethane foams with reduced flammability based on new phosphorus-and nitrogen-containing diols

Abstract Phosphorus- and nitrogen-containing diols (aminomethylphosphine oxides) have been used to prepare rigid polyurethane foams (PUF) with various phosphorus contents. Some characteristic properties of the PUF have been examined. The effects of structure and the amount of phosphorus- and nitrogen-containing diols on properties of the polyurethanes, especially on their resistance to combustion, have been studied. The phosphorus- and nitrogen-containing diols are effective flame retardants for improving the resistance to combustion of rigid PUF (ASTM D-2863 and ASTM D-1692). It is also concluded that the phosphorus present in these diols is up to a certain extent more effective than the phosphorus present in the commercially available diol Fyrol 6.

THE REACTION OF DIMETHYL HYDROGEN PHOSPHONATE AND AMINOALCOHOLS

Abstract The interaction between dimethyl hydrogen phosphonate (DMHP) and aminoalcohols was examined. It was found that at the temperature of 80°C the basic reaction is that of alkylation of the aminoalcohols. The structure of the end products was proved by the aid of 1H- and 31P-NMR spectroscopy.

Phosphorus-containing rigid polyurethane foams—II. Modifiers based on trimethyl phosphate

Abstract Phosphorus-containing modifiers, alkanolammonium salts, obtained by interaction of trimethyl phosphate and aminoalcohols, are used to obtain rigid polyurethane foams (PUFs) with various phosphorus contents. Some of their physical mechanical properties and resistance to combustion are examined. It is shown that these phosphorus-containing modifiers are effective additives for improving fire resistance of rigid PUFs. For a low concentration of phosphorus-containing modifier, the rigid PUFs have high fire resistance and good physical and thermomechanical properties.