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. 2021 Mar 3;13(5):778.
doi: 10.3390/polym13050778.

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

Olga Kokkorogianni  1 , Philippos Kontoes-Georgoudakis  1 , Maria Athanasopoulou  1 , Nikolaos Polizos  1 , Marinos Pitsikalis  1
Affiliations

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

Olga Kokkorogianni et al. Polymers (Basel). .

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.

Keywords: N-vinylpyrrolidone; RAFT; isobornyl methacrylate; reactivity ratios; statistical copolymers; thermal properties.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthesis of PNVP-stat-PIBMA statistical copolymers.
Figure 1
Figure 1
SEC chromatograms of the samples (a) F80/20 and (b) R80/20.
Figure 2
Figure 2
1H-NMR spectrum of the sample F60/40 in CDCl3.
Figure 3
Figure 3
Dyad sequence distributions for the PNVP-stat-PIBMA copolymers via free radical copolymerization: (•): Μ(IBMA)-M(IBMA), (■): Μ(NVP)-M(NVP), (▲): Μ(NVP)-M(IBMA).
Figure 4
Figure 4
(a): TGA thermograms for the PIBMA under different heating rates. (b): DTG thermograms for the PIBMA under different heating rates.
Figure 5
Figure 5
(a): TGA thermograms for the sample R20/80 under different heating rates. (b): DTG thermograms for the sample R20/80 under different heating rates.
Figure 6
Figure 6
(a): TGA thermograms for the sample R40/60 under different heating rates. (b): DTG thermograms for the sample R40/60 under different heating rates.
Figure 7
Figure 7
Kissinger plots for the PIBMA.
Figure 8
Figure 8
Kissinger plots for sample R40-60.
Figure 9
Figure 9
OFW plots for PIBMA.
Figure 10
Figure 10
OFW plots for sample R20-80.
See this image and copyright information in PMC

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