Phosphorus trichloride, polycondensation

Polycondensation of D-glucose also followed when a mixture of D-glucose (20 g.) and water (2 ml.) was heated at 95° with phosphorus trichloride (13), phosphorus pentachloride (14), or phosphorus pentaoxide (15), 82 The addition of water was essential, since these three compounds apparently failed to catalyze polycondensation under anhydrous conditions. Under optimum conditions, polymers of Pn 11-13 were obtained in 10-15% yield after 20-30 min. reaction times, when (13) and (14) were used for catalysis. With (15), polymers of Pn 8-11 were obtained in 10-30% yield, but such polycondensations required 1-2 hr., instead of a few minutes (as for 13 and 14). In no case did polymerization appear to be as efficient as when sulfuric acid was used. 

The Elf Aquitaine process is quite different because it is based on the polycondensation reaction of dichlorophosphoryltrichlorophospha-zene C13P=N—P(Cl2)=0, the latter being prepared from ammonium sulfate phosphorus trichloride and chlorine [190,191], This condensation re-... 

Various polyesters derived from phosphorous or phosphoric acids were prepared. Efiicient polyphosphites were synthesised in the early 196(. Polyphosphite prepared from 152 and 4,4 -isopropylidenebis(cyclohexanol) was tested as a thermal stabilizer for PC [199] or as secondary AO for radiation sterilized EPM [200]. Built-in phosphites obtained by transesterification of triallcylphosphite with 4,4 -isopro-pylidenebisphenol or 4,4 -thiobisphenol possess antioxidant properties in polyolefins. Stabilizer containing phosphite moiety 153 was prepared from tris(2-hydroxy-ethyl)isocyanate, decyl alcohol and triphenylphosphite [201]. Various phosphites were derived firom polynuclear phenols or dihydric phenols. For example, a polycondensate prepared by reaction of phosphorus trichloride with 2,5-di-rert-butylhydroquinone was tested as heat and light stabilizer for PP [202], A linear polyester with a built-in phenolic moiety was synthesised from (2,6-di-tm-butyl-4-methylphenyl)bis(6-hydroxyhexyl)phosphite and dimethyl terephthalate [203]. 

Aromatic Polyamides.— The synthesis of aromatic polyamides in the disperse phase from phenylene diamine and aromatic diacid chlorides has been reviewed, as has direct polycondensation in the presence of triphenyl phosphite prepared in situ from phenol and phosphorus trichloride in excess of pyridine. ... 

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