Synthesis of new linear polymers containing phosphorus atom in the main chain by the radical polyaddition: Addition polymers of phenylphosphine with 1,4‐divinylbenzene or 1,4‐diisopropenylbenzene and their properties

Abstract

AbstractA polyaddition of phenylphosphine (PH) to 1,4‐divinylbenzene (DVB) or 1,4‐diisopropenylbenzene (DIPB) was carried out by radical initiations or UV irradiation at 60–80°C in toluene under a nitrogen atmosphere. The soluble polymer with higher molecular weight ($\[ \bar M_w = 2 \times 10^4 \]$) was obtained in a high yield with AIBN initiator for 95 h in the presence of 5% excess of PH to DVB (monomer feed ratio [DVB]0/[PH]0 = 1/1.05). On the other hand, a polyaddition of PH to DIPB proceeded much slower than the case of DVB, but the high polymer was obtained in a high yield by choosing polyaddition conditions such as polyaddition temperature and initiator concentration. From 1H‐NMR, IR analyses, and phosphorus content of the polymers, it was characterized that both polymers have the alternating structure consisting of PH and DVB or DIPB units in 1 : 1 ratio. The glass transition and decomposition temperatures of both polymers under a nitrogen atmosphere were almost similar: 15–30°C and 380–385°C, respectively; but, the polymers were oxidized by heating under an atmosphere of air. The polymers had a self‐extinguishing property and the polymer blend of the flammable polymers such as polystyrene and polyethylene with the phosphorus‐containing polymers exhibited an excellent flame resistance. © 1994 John Wiley & Sons, Inc.