화학공학소재연구정보센터
Reactive & Functional Polymers, Vol.30, No.1, 309-315, 1996
Synthesis of fluorine-containing polyphosphates: Low-temperature solution polycondensation of bisphenol AF and aryl phosphorodichloridates
This paper describes the synthesis of aromatic polyphosphates from the reaction of various aryl phosphorodichloridates with bisphenol AF in a chlorinated hydrocarbon solvent under low-temperature conditions. The polyphosphates obtained were characterized by IR, C-13- and P-31-NMR spectra, elemental analysis, inherent viscosity, TGA, DSC, X-ray diffraction, LOI, contact angle and molar mass measurement. All the polyphosphates obtained had high yields and the inherent viscosities were in the range 0.25-0.31 dl g(-1). The weight average molar masses ((M) over bar(w)) were in the range 0.96 x 10(4) - 1.33 x 10(4) with relatively narrow molar mass distributions ((M) over bar(w)/(M) over bar(n) = 1.2-1.4). All the polymers, except polymer C, are stable up to 250 degrees C, exhibited 10% loss of mass at 417-463 degrees C, and had 20-30% residual mass at 700 degrees C in nitrogen. The X-ray diffraction patterns revealed that all the polyphosphates are semicrystalline and polymer E, containing a flexible ether linkage, has a relatively large degree of crystallinity. The fluorine-containing polyphosphates have glass-transition temperatures between 81-108 degrees C and polymer C, having a NO2 group in the side chain phenyl ring, has the highest T-g value. The polyphosphates obtained from bisphenol AF showed better thermal stabilities and higher LOI values than those obtained from bisphenol A. The polyphosphates have good flame retardancy, as indicated by high limiting oxygen index values in the range of 47-60. The water contact angles (theta(w)) of all polyphosphates are in the range of 76-109 degrees. The contact angles of polymers A and B are larger than other polyphosphates which contain more oxygen content or bromine atoms (polymers C, D and E).