Synthesis and Aqueous Solution Properties of an Amino Bisphosphonate Methacrylate Homopolymer via RAFT Polymerization

Polymers (Basel). 2018 Jun 27;10(7):711. doi: 10.3390/polym10070711.


The present contribution reports on the synthesis via reversible addition-fragmentation chain transfer (RAFT) polymerization of a methacrylate derivative bearing an aminobisphosponate moiety as a pendant group, namely, ethyl N,N-tetramethylbis(phosphonate)-bis(methylene) amine methacrylate (MAC₂NP₂). The polymerization was performed by the use of cyanoisopropyl dithiobenzoate as chain transfer agent at 70 °C in various solvents with different polarities including N,N-dimethylformamide, acetonitrile, tetrahydrofuran, and in bulk. Best results were obtained in N,N-dimethylformamide where higher conversions and polymerization rates were noticed. The successful hydrolysis of the phosphonate ester groups was performed using bromotrimethylsilane with excellent yields leading to the formation of highly water soluble and pH-responsive polymers. Finally, a preliminary solution behavior study was carried out by investigating the aqueous solution properties of synthesized amino bisphosphonate methacrylate homopolymers and their phosphonic acid analogs via potentiometric titration and zeta potential measurements.

Keywords: RAFT polymerization; amino bisphosphonate; amino bisphosphonic acid; hydrolysis; pH-responsive polymers; solvent polarity.