Statistical Copolymers of N-Vinylpyrrolidone and Isobornyl Methacrylate via Free Radical and RAFT Polymerization: Monomer Reactivity Ratios, Thermal Properties, and Kinetics of Thermal Decomposition

Abstract

The synthesis of statistical copolymers of N-vinylpyrrolidone (NVP) with isobornyl methacrylate (IBMA) was conducted by free radical and reversible addition-fragmentation chain transfer (RAFT) polymerization. The reactivity ratios were estimated using the Finemann-Ross, inverted Fineman-Ross, Kelen-Tüdos, extended Kelen-Tüdos and Barson-Fenn graphical methods, along with the computer program COPOINT, modified to both the terminal and the penultimate models. According to COPOINT the reactivity ratios were found to be equal to 0.292 for NVP and 2.673 for IBMA for conventional radical polymerization, whereas for RAFT polymerization and for the penultimate model the following reactivity ratios were obtained: r11 = 4.466, r22 = 0, r21 = 14.830, and r12 = 0 (1 stands for NVP and 2 for IBMA). In all cases, the NVP reactivity ratio was significantly lower than that of IBMA. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length. The thermal properties of the copolymers were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and differential thermogravimetry (DTG). The results were compared with those of the respective homopolymers.

A self-crosslinking monomer, α-pinene methacrylate: understanding and exploiting hydrogen abstraction

“…All the polymerisations were carried out using AIBN at 65 °C and in all the cases solidification of the reaction mixture was observed. This behaviour was expected considering the high glass transition temperatures of the three growing polymer chains, 105–120 °C for PMMA, 110–200 °C for PIBMA 48 and 85–168 °C for PαPMA 24,25 (depending upon reaction conditions and thermal analysis approach). The main difference observed was the time at which each sample became completely solid.…”

Statistical Copolymers of N–Vinylpyrrolidone and 2–Chloroethyl Vinyl Ether via Radical RAFT Polymerization: Monomer Reactivity Ratios, Thermal Properties, and Kinetics of Thermal Decomposition of the Statistical Copolymers

“…The thermal stability and the kinetics of the thermal degradation of the statistical copolymers were investigated employing TGA and DTG measurements. According to the literature, the PNVP homopolymer exhibits a one-step thermal decomposition process at temperatures ranging from 416 • C to 453 • C [12]. Conversely, the PCEVE homopolymer has far more complicated thermal degradation behavior.…”

“…Due to its solubility in water, the copolymerization with hydrophobic monomers can lead to the synthesis of amphiphilic materials. In fact, the synthesis of statistical copolymers based on NVP and various methacrylates has been reported in the literature, with the hydrophobic character predominating in each case due to the higher reactivity of the methacrylates [9][10][11][12][13]. Other more complex amphiphilic or double hydrophilic architectures have appeared in the literature [14].…”

Recent Advances in the Synthesis of Complex Macromolecular Architectures Based on Poly(N-vinyl pyrrolidone) and the RAFT Polymerization Technique

“…In a series of publications, the synthesis of statistical copolymers of NVP with various methacrylates was presented in an effort to trace the best copolymerization model, which efficiently describes the copolymerization process, to calculate the reactivity ratios of the comonomers and to study the structural characteristics of the copolymers. The most recent project described the synthesis of statistical copolymers of NVP with isobornyl methacrylate, IBMA [51], which was conducted at 60 • C by using AIBN as initiator, [(Oethylxanthyl)methyl]benzene as CTA and 1,4-dioxane as solvent. The polymers were precipitated in cold methanol.…”