A number of phosphorus-based monomers have been evaluated by free radical polymerization or photopolymerization, but fewer examples have been involved in the “living”/controlled radical polymerization (LRP) of such type of monomers, whereas LRP techniques allow the synthesis of well-defined polymers with designable structures, compositions and properties. In this work, a novel methacrylate based monomer with a bisphosphonate group 4-(bis(diethoxyphosphoryl)methyl)phenyl methacrylate (BPMA) was synthesized first and then polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymerization showed typical “living” features such as the polymerization, which indicates first order kinetics with respect to monomer concentration, and the molecular weights of the resultant polymers increase with monomer conversion. Furthermore, the resultant polymers demonstrated better thermal and flame-retardant properties. According to the thermal gravimetric analyzer (TGA) test, the amount of residual carbonaceous mass (char) increased with the molecular weight of the resultant polymers. Furthermore, the micro-scale combustion calorimetry (MCC) test also confirmed its superior flame-retardant performance.
A novel phosphonic acid and triazolyl functionalized poly(ether sulfone) (PES-TriPA) containing simultaneously phosphonic acid and triazolyl side groups is synthesized. The PES-TriPA is prepared by polycondensation of phosphonated bisphenol (PBP) and 3,3′-diethynyl-4,4′-difluorodiphenylsulfone, followed by click reaction to introduce triazolyl groups and hydrolysis to free phosphonic acid groups. Phosphonic acid functionalized poly(ether sulfone) (PES-PA) and triazolyl functionalized poly(ether sulfone) (PES-Tri) are also synthesized for comparison with PES-TriPA. The proton conducting polymers are hot-pressed into proton exchange membranes , and the membrane morphologies, proton conductivities , oxidation and thermal stabilities, water uptakes and methanol permeabilities are characterized. PES-TriPA exhibits more excellent comprehensive properties in comparison with PES-PA and PES-Tri. At 100 °C and 90% relative humidity (RH), the proton conductivity of PES-TriPA reaches 113.0 mS cm −1 , in comparison with 55.7 mS cm −1 for PES-PA and 4.3 mS cm −1 for PES-Tri. PES-TriPA also shows better oxidation stability with 95.7% weight left after Fenton's test at 80 °C for 120 h, while only 68.7% left for PES-PA and 75.7% left for PES-Tri. In addition, PES-TriPA exhibits favorable thermal stability and water uptake compared with PES-PA and PES-Tri. Moreover, the methanol permeability of PES-TriPA is only 0.24 × 10 −8 cm 2 s −1 , which is lower than these of PES-PA and PES-Tri with 0.77 × 10 −8 cm 2 s −1 and 1.20 × 10 −8 cm 2 s −1 , respectively. These superior characteristics are attributed to the synergetic effect between the phosphonic acid groups and triazolyl groups caused by the intermolecular hydrogen bonding interaction throughout the PES-TriPA acid-base amphoteric polymer.
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