The synthesis, characterization, thermal, and dielectric properties of three different zwitterionic methacrylates of the sulfobetaine type are presented. Diethylamine‐ethyl‐, 2‐(diethylaminoethoxy)‐ethyl‐, and 2‐(2‐diethylaminoethoxy) ethoxy‐ethyl‐methacrylates were made to react with butanosultone to prepare monomers with variable flexibility. The flexibility of the lateral chain of the polymethacrylates decreased the glass transition temperature (Tg down to 300 K) of the polymers. A linear relationship between Tg and the number of carbon atoms was shown for these materials. X‐ray diffraction and DSC experiments showed the formation of new ordered phases in these polymers, which inhibited their dipole conductivity. On heating, these phases were destroyed and values of conductivity of 10−7–10−3 S cm−1 were obtained in the studied range of temperature. Variation of conductivity with temperature was established according to the Arrhenius equation. Dielectric properties exhibited a small deviation of the Debye type behavior, and β parameters of the Cole–Cole equations were calculated for the synthesized polymers. © 1997 John Wiley & Sons, Inc.

Homo and copolymerization of isoprene with small amounts (1–10 wt %) of glycidyl methacrylate (GMA) are conducted using controlled‐living radical polymerization mediated by nitroxides at 120 °C and 1170 kPa in solution with toluene (30 wt % solids). N‐tert‐butyl‐N‐(2‐methyl‐1‐phenylpropyl)‐O‐(1‐phenylethyl) hydroxylamine is successfully used as a control agent (unimolecular process) although other controllers are also tested (TIPNO and OH‐TEMPO in a bimolecular process using BPO as initiator). Chain extension experiments demonstrate the livingness of the synthesized materials. Several additives (acetic anhydride, camphorsulfonic acid and glucose) prove effective in accelerating the reactions. All the successful polymerizations result in first‐order kinetics with respect to the monomer, yielding average molecular weights (Mn) of about 75% compared to the theoretical Mn (Mn, theo) with dispersities (Ð) ranging from 1.2 to 1.7 depending on the agent used for control. Controlled grafts of poly(isoprene‐co‐GMA) are also attached to polyisoprene via nitroxide chemistry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45108.

Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (kh)]. At higher TEMPO concentrations ([N•] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition kad, also becomes relevant. From previous experimental data and simulations, initial estimates of kh ≈ 1 and kad ≈ 6 × 10−7 L mol−1 s−1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression kth[M]3 (where [M] is the monomer concentration and kth is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006

Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, kc[P][N] = kd[PN], where P, N and PN are living, nitroxide radicals and dormant species respectively, with kinetic constants kc and kd, is found valid only for small values of the equilibrium constant K (10−11–10−12 mol · L−1) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, kc[P][N] = kd[PN]0 was found to be remarkably good up to values of K around 10−8 mol · L−1. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.imageValidity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.

Recently we reported an experimental and theoretical (simulation) investigation on the mechanism of the induction period and the initial polymerization stages in the nitroxide mediated autopolymerization of styrene. In this paper we extend some of the results presented there and perform preliminary induction period experiments for the study of the mechanism and kinetics of the spontaneous copolymerization of styrene (S) and maleic anhydride (MA) in the presence of TEMPO and 4‐OH‐TEMPO. With even small amounts of MA (2% wt) the induction period is dramatically reduced by a factor of about 20 in comparison with the nitroxide‐mediated styrene autopolymerization at 120 °C. Our results suggest that the initiation mechanism involves a first step of reaction between S and MA. We speculate that this reaction is a Diels‐Alder cycloaddition followed by hydrogen abstraction through a monomer or TEMPO assisted homolysis to form a radical pair (monomer case) or a single radical (TEMPO case), which either initiates polymerization or is trapped by TEMPO depending on the conditions. Hall and Padias have studied similar electron donor‐acceptor co‐monomer pairs and favor the formation of a tetramethylene diradical as the initiating species for spontaneous copolymerization. In any case, the rate‐limiting step would be the initial reaction of S and MA. These induction experiments allow us to obtain an initial estimate of the order of magnitude for the kinetic constant of the rate‐limiting step, as 10−6 Lmol−1s−1.