Synthesis and Radical Polymerization of Methacrylate Monomers Containing Cyclotriphosphazene. Thin-Layer Grafts of Their Polymers on a Poly(vinyl alcohol) Surface

Abstract

The reaction between the monohydroxylated cyclotriphosphazene (4-hydroxyphenoxy)pentaphenoxycyclotriphosphazene, 3obtained by the reaction of the (4-methoxyphenoxy)pentaphenoxycyclotriphosphazene 2 with BBr3/H2Oand methacryloyl chloride, led to a new methacrylate-substituted cyclotriphosphazene, 4. Radical polymerization of 4 led to the hybrid inorganic−organic poly(cyclophosphazene−methacrylate) 5. The structures of both classes of compounds were investigated by 31P, 13C, and 1H NMR, infrared spectroscopy, mass spectrometry, size exclusion chromatography, and elemental analysis. The thermal behavior of the new polymer 5 was investigated and compared to the one of poly(phenyl methacrylate) 6. It was demonstrated that the incorporation of cyclophosphazene as pendant group increases the thermal stability of the corresponding organic polymer. The free-radical promoted grafting of 5 onto poly(vinyl alcohol)surface has been described. The resultant surfaces were studied by ATR-IR, XPS, and contact angle techniques. It was demonstrated that the presence of ethyl functions in 5 increases the grafting yield.

Phosphazenes and Surfaces

“…Surface Functionalization of PVA and EVOH Polymer Films Basic investigations of the surface functionalization of PVA and EVOH films carried out by De Jaeger and colleagues [162][163][164][165][166], who considered these materials because of the excellent gas barrier properties of PVA in its dry state, which become very poor under moister conditions [163]. For this reason the surfaces of PVA films were treated with a variety of products to reach the grafting of some phosphazene copolymers containing different functional groups, all of them showing good hydrophobic features.…”

“…For this reason the surfaces of PVA films were treated with a variety of products to reach the grafting of some phosphazene copolymers containing different functional groups, all of them showing good hydrophobic features. Under these conditions the ethyl group present in the para position of the phenoxy substituent in the cyclophosphazene is able to react with the PVA surface and induce grafting of the cyclophosphazene-methacrylate polymer onto the surface of PVA [164], thus forming a coating layer on this polymer. Thus, poly[(phenoxy)(4-ethylphenoxy)(2-methyl-4-allylphenoxy)phosphazene] (Scheme 27), a phosphazene copolymer containing free allylic moieties, was grafted onto the surface of PVA by treating this substrate with a toluene solution of the polyphosphazene at 80-1101C in the presence of benzoylperoxide as a radical initiator [162] (pathway a, Scheme 26).…”

Ring-Opening Metathesis Polymerization of Phosphazene-Functionalized Norbornenes

“…Polymers that contain phosphazene units fall into three categories. First and most numerous are macromolecules with a backbone of alternating phosphorus and nitrogen atoms and with two organic side groups attached to phosphorus. − Second are the cyclolinear and cyclomatrix polymers in which phosphazene ring units are linked by difunctional organic moieties. ,, The present work falls into the third group which consists of organic polymer chains to which are attached cyclic phosphazene side groups. − …”

“…1,2,5 The present work falls into the third group which consists of organic polymer chains to which are attached cyclic phosphazene side groups. [6][7][8][9] Most of the research on organic polymers with cyclophosphazene side groups has been conducted by Allen and co-workers, who developed a series of vinyl-and allyl-substituted cyclophosphazenes which were then polymerized by addition reactions. [10][11][12] In this paper we report an alternative approach to polymers of this type which involves the ring-opening metathesis polymerization (ROMP) of norbornenes that bear cyclophosphazene pendent groups.…”

Surface Functionalization with Phosphazenes, Part 3: Surface Modification of Plasma-Treated Polyethylene with Fluorinated Alcohols Using Chlorinated Phosphazenes as Coupling Agents

“…On the contrary, surface modification of conventional organic polymeric materials using poly(organophosphazenes) has been achieved basically by two different synthetic approaches, i.e., surface coating , and surface grafting reactions of different phosphazene macromolecules on poly(ethylene), poly(propylene), poly(vinyl chloride), poly(ethylene terephthalate), poly(bisphenol A carbonate), poly(methylmethacrylates), poly(vinyl alcohol), − poly(ethylene-co-vinyl alcohol), and on carbon black …”