Phosphine oxide polyols

Due to the high cost of the raw materials and of the final product, the manufacture of this phosphine oxide polyol was stopped [42]. 

Very interesting reactive flame retardants were used successfully in the fabrication of flame retardant rigid PU foams by Solvay under the name of Ixol polyols. These polyols are triols based on epichlorohydrin and brominated unsaturated diol. Ixol polyols have chlorine, bromine and phosphorus in each structure [3, 44, 45]. 

Very interesting new reactive flame retardants were developed by Borissov and Jedlinski [12, 43, 45-50]. A new phosphine oxide polyol is based on tetrakis (hydroxymethyl) phosphonium chloride as 80% aqueous solution. The reactions involved in the synthesis of this phosphine oxide polyol, bis(hydroxymethyl)-N,N-bis(2-hydroxyethyl) aminomethylphosphine oxide [45], are presented below  

---

Phosphine oxide has three hydrolysis resistant -P-C- bonds. A phosphine oxide polyol, extremely resistant to hydrolysis (Figure 18.6), was used for a short period of time but due to economic reasons the production was stopped [40-43]. 

Isobutyl bis(glycidylpropylether) phosphine oxide [77], oligomeric polyalkyl phosphate polyols [64], triacryloyloxyethyl phosphate (TAEP), diacryloyloxyethyl ethyl phosphate (DAEEP) [80] and phosphate methacrylate [80-82] have all been used to improve the flame retardancy of alkyl phosphate type polymers. 

An infrared method for the analysis of primary alcohols in polyglycols based on the reaction of the polyol with triphenylchloromethane is where the reagent consists of trityl chloride, with tris(dimethyl amino)phosphine oxide in quinoline as a solvent. This reagent is added to the sample, scanned from 3700 to 3100 cm to establish the total hydroxyl absorbance, and the reaction is then carried out in a glass-stoppered flask in a thermostatted bath at 75°C. At appropriate times, aliquots are removed and scanned, the absorbance being measured at 3280cm... 

A diol containing a phosphine oxide structure was shown to be useful in urethane coatings, adhesives, and rigid foams (204). Advantages included shelf stability of the amine catalysl>-polyol mixture, low smoke, and good resistance to humidity (205). 

To circumvent the formation of ditelomers and to attempt recycling of the catalysts, the telomerization of polyols was studied in the presence of water using water soluble catalysts such as Pd/TPPTS (TPPTS = tris(m-sulfonato-phenyl) phosphine trisodium salt) [9, 12, 16, 17]. Behr et al. studied the telomerization of ethylene glycol under biphasic conditions. Under such reaction conditions, 80% of mono-telomer are formed and only traces of ditelomer and butadiene dimers are detected (Fig. 4). This is attributed to the solubility of the monomer in the catalyst phase. However, the catalyst is unstable and decomposes rapidly, leading to almost inactive catalyst after three runs. This is due to TPPTS oxidation during the work-up of the reaction and can be avoided by addition of 2.5 equiv. ligand in the solution prior to each run. 

---