Syntheses and properties of poly(diethyl vinylphosphonate) initiated by lanthanide tris(borohydride) complexes: Polymerization controllability and mechanism

Abstract

Polymerization of diethyl vinylphosphonate (DEVP) is achieved by using lanthanide tris(borohydride) complexes, Ln(BH4)3(THF)3 (Ln = Y, La, Nd, Sm, Gd, Dy, Lu) as an initiator. The characteristics and mechanism of polymerization as well as the properties of the resulting poly(diethyl vinylphophonate)s (PDEVPs) are studied. The effects of the lanthanide elements, the molar ratios of monomer to initiator ([M]/[ln]), reaction temperature and time on polymerization have been investigated in detail. The optimized polymerization conditions are 40 °C, 1 h in bulk with [M]/[ln] = 300. The kinetic study indicates that the polymerization of DEVP undergoes a controlled manner as the molecular weights (MWs) of PDEVPs increase with monomer conversion linearly maintaining moderate MW distribution (1.7–1.9). Additionally, a coordination anionic polymerization mechanism is proved by end‐group analysis with ESI mass and 1H NMR spectroscopy. The obtained PDEVPs have low glass transition temperature (Tg = −62 °C) and high thermal decomposition temperature (Td > 300 °C) determined by differential scanning calorimetry and thermogravimetric analysis respectively. The thermosensitive behavior of PDEVP is characterized by evaluating the lower critical solution temperature of PDEVP in water by ultraviolet transmittance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2409–2415

Polypeptoids with tunable cloud point temperatures synthesized from N-substituted glycine N-thiocarboxyanhydrides

“…Many of these polymers have a lower critical solution temperature (LCST) or a cloud point temperature (T cp ) in water, which is promising for various biological applications. [6][7][8] Different kinds of thermoresponsive polymers have been comprehensively investigated in the past few decades, including poly-(ethylene glycol) (PEG), 9 poly(N-isopropylacrylamide) (PNIPAM), 10,11 poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), 12,13 poly(N-vinyl caprolactam) (PNVCL), 14 poly-(diethyl vinylphosphonate) (PDEVP), 15,16 poly[(oligo-ethylene glycol)…”

Thermosensitive t -PLA-b -PNIPAAm tri-armed star block copolymer nanoscale micelles for camptothecin drug release

“…Since the micellization behavior of block copolymers in aqueous solution was found by Tuzar and Kratochvíl in 1976, block copolymers, especially amphiphilic block copolymers have widely been studied. This copolymer generally contains hydrophilic and hydrophobic segments, and hence can self‐assemble into core‐shell nanoscale micelles in aqueous solution by hydrophobic, electrostatic, metal complexation, or hydrogen bonding interactions . The lipophilic core can effectively dissolve water‐insoluble substances, and the hydrophilic shell can retain the micelles stable in aqueous solution.…”

Design, Synthesis and Actual Applications of the Polymers Containing Acidic P–OH Fragments: Part 2—Sidechain Phosphorus-Containing Polyacids

“…Note that in 2013 [ 92 ], Ni and Coll. have demonstrated high catalytic activity of Ln(BH 4 ) 3 (THF) 3 (Ln = Y, La, Nd, Sm, Gd, Dy, Lu) in group transfer polymerization of CH 2 =CHP(O)(OEt) 2 .…”