Polymerization behavior of novel vinyl monomers containing pyrrolidone moieties

Abstract

Homopolymerization of novel pyrrolidone-containing vinyl monomers, 4-[(2-oxo-l-pyrrolidinyl)methyl] styrene (PS) and 4-[ [ 2-(2-oxo-1 -pyrrolidinyl) ethoxy] methyl] styrene (PES), and their copolymerizations with styrene (St), p-methoxystyrene (PMS), and m-hydroxystyrene (MHS) were investigated. The polymerization behavior of PS and PES [P(E)S] was compared with that of oxazolidone-containing vinyl monomers.Polymerization of PS at a high monomer concentration gave gelled polymer, while in the polymerization of PES soluble polymer was obtained without any gelled polymer even in bulk condition.Copolymerizations of P(E)S with styrene derivatives were carried out to estimate copolymerization parameters which were obtained by both nonlinear least-squares (NLLS) and Fineman-Ross methods (FR). The alternating copolymerizability decreased in the order St > PMS > MHS, which was suggested to result from the difference in strength of the interaction between pyrrolidone moieties and aromatic groups of styrene derivatives. The copolymerization behavior of P(E)S with MHS was compared with that of 4-[(2-oxo-3-oxazolidinyl)methyl]styrene (OS) and 4-[[2-(2-oxo-3-oxazolidinyl)ethoxy]methyl]styrene (OES). The alternating copolymerizability of P(E)S with MHS was superior to that of 0(E)S with MHS. From the spectroscopic study such as NMR and IR, the difference of the copolymerization behavior was dependent on the interaction between P(E)S-MHS and 0(E)S-MHS. It was suggested that the interaction between the oxazolidone moiety and phenolic group is attributed only to hydrogen bonding while that between the pyrrolidone moiety and phenolic group comes from the both hydrogen bonding and C-T stacking.

Synthesis of Polymers Containing the Pendant Oxazolidone Moiety and Their Complex-Forming Behavior with Phenols

“…1 in chloroform14 in accordance with the above systems. 10 The clear solvent dependency of n values would be accounted for by assuming a hydrophobic interaction, an extra interaction which can be seen in water but not in chloroform, as described in the following discussion on the binding constant (K), Namely, the site-density value pKa Figure 4. Plots of log K vs pK, of the phenols (data in chloroform in Table 1).…”

“…Although the oxazolidone moiety can also interact with phenols, its strength seems to be smaller than that of the pyrrolidone moiety from the results of the radical copolymerization behavior of vinyl monomers carrying such a moiety with m-vinylphenol. 11 It is interesting to investigate the effect of spacer length in the oxazolidone system and compare 1 Japan Tobacco Inc.…”

Synthesis and Solution-state Assembly or Bulk State Thiol-ene Crosslinking of Pyrrolidinone- and Alkene-functionalized Amphiphilic Block Fluorocopolymers: From Functional Nanoparticles to Anti-fouling Coatings

“…Poly(N-vinyl pyrrolidinone) (PNVP), a water-soluble, anti-fouling, and biocompatible polymer, [12][13][14] has been shown recently to be prepared by CRP of N-vinyl pyrrolidinone (NVP), although its polymerization is challenging. [12,15,16] An alternative strategy involves incorporating the Py moiety onto a pre-existing, readily-polymerizable monomer, such as styrene [17] or methacrylate. [18][19][20] Therefore, the polymerizations and block copolymerizations of three bifunctional monomers were investigated, each derived from 2,3,4,5,6-pentafluorostyrene (PFS), with two bearing hydrophilic Py units and one presenting a hydrophobic vinylic substituent.…”