Statistical copolymerization of N-vinyl-pyrrolidone and alkyl methacrylates via RAFT: reactivity ratios and thermal analysis

Mitsoni, Eleftheria; Roka, Nikoletta; Pitsikalis, Marinos

doi:10.1007/s10965-019-1776-7

Cited by 14 publications

(14 citation statements)

References 49 publications

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“…It is obvious that conducting the copolymerization of the same monomers with different methodologies, namely conventional free radical and RAFT, results in different copolymerization behavior, which can be described by different copolymerization models. This effect has been verified in the literature using as monomers NVP and n-hexyl methacrylate [52,53].…”

Section: Statistical Copolymers Of Nvp and Ibma Via Raft Polymerizationsupporting

confidence: 65%

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

et al. 2021

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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.

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Section: Statistical Copolymers Of Nvp and Ibma Via Raft Polymerizationsupporting

confidence: 65%

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

et al. 2021

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“…Parameter upper and lower bounds are also inputted at this point. The inner loop then calculates the true value of the variables for the next step using Equations (11) and 12…”

Section: The Evm Algorithmmentioning

confidence: 99%

“…[ 7 ] Such methods, however, have been found to alter the error structure of the collected data, giving statistically incorrect results, [ 8 ] and are still in use to this day. [ 9–14 ] This problem was solved with the use of nonlinear parameter estimation techniques, such as the error‐in‐variables method (EVM), which are based on sound statistical theory (Bayesian approach) and return parameter estimates with joint confidence regions. [ 15,16 ] For metallic catalyzed copolymerizations the ratios can be calculated by directly using monomer kinetic propagation parameters combined with specialized molecular weight distribution deconvolution software.…”

Section: Introductionmentioning

confidence: 99%

Reactivity Ratios Estimation of the Free‐Radical Polymerization of Itaconic Acid and N‐Vinyl‐2‐Pyrrolidone by the Error‐in‐Variables Methodology

Krieger¹,

Araújo²,

Sayer³

2020

Macro Reaction Engineering

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commonly used method for determining the reactivity ratios of a copolymerization reaction is by linearization of the Mayo-Lewis equation, such as those first pioneered by Fineman and Ross [6] and Kelen and Tudos. [7] Such methods, however, have been found to alter the error structure of the collected data, giving statistically incorrect results, [8] and are still in use to this day. [9-14] This problem was solved with the use of nonlinear parameter estimation techniques, such as the error-in-variables method (EVM), which are based on sound statistical theory (Bayesian approach) and return parameter estimates with joint confidence regions. [15,16] For metallic catalyzed copolymerizations the ratios can be calculated by directly using monomer kinetic propagation parameters combined with specialized molecular weight distribution deconvolution software. [17] Part of the reason for why methods such as Fineman-Ross and Kelen-Tudos are still used to this day is not only due to their ease of use and traditional weight but also because of a lack of widespread and publicly available alternatives that can be used and modified freely to tackle specific problems. This work seeks to lessen the lack of availability of these more statistically sound methods so that others may use and further contribute to their development in a free environment, in particular of EVM. Besides the reports of the groups who worked on the early development of EVM, [18-21] other groups worked on their own implementations of EVM. [22-24] None of these codes is easily accessible. Poly[(itaconic acid)-co-(N-vinyl-2-pyrrolidone)] (PVPIA) is reported as being a hydrophilic, highly biocompatible copolymer [25] that, when synthesized in the presence of a crosslinker or through UV or gamma-ray irradiation, produces a crosslinked hydrogel that may present swelling rates of up to 1500%. [26] It can be used as a heavy metal ion remover in waste-water treatment, [27,28] as an enzyme immobilization support structure, [29] and as a medium for the controlled release of drugs. [30] It is also worth noting that except for applications as a heavy metal ion remover in waste-water treatment, [27,28] the Itaconic Acid content used was below 10% (between 3% and 8%) of the total initial monomer charge. However, reports of the copolymer when prepared through free radical chain polymerization are severely limited and so are descriptions of its physical properties and possible applications. Designed copolymers require an understanding of the relative reactivity ratios of the monomer pair and a proper regression technique that can extract this data from the experiments. An implementation of the error-in-variables method previously describes in the literature is written and made available for use, along with an high-performance liquid chromatography (HPLC) methodology for acquiring the kinetic data for the regression analysis of the itaconic acid and N-vinyl-2-pyrrolidone (IA/NVP) free-radical copolymerization system. From the data, it is observed that higher initial mole fract...

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“…In this work, statistical copolymers of N-vinylpyrrolidone (NVP) with the alkyl methacrylates, hexyl methacrylate (HMA) and stearyl methacrylate (SMA), were used. In a previous study, the copolymerization behavior of NVP with either HMA or SMA was studied with regard to terminal and the penultimate copolymerization models [40].…”

Section: Introductionmentioning

confidence: 99%

Thermal Stability and Kinetics of Thermal Decomposition of Statistical Copolymers of N-Vinylpyrrolidone and Alkyl Methacrylates Synthesized via RAFT Polymerization

Gikarakis

Pappas

Arvanitaki

et al. 2021

Journal of Chemistry

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The thermal stability and the kinetics of thermal decomposition of statistical copolymers of N-vinylpyrrolidone (NVP) with the alkyl methacrylates, hexyl methacrylate (HMA) and stearyl methacrylate (SMA), were studied by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG). Statistical copolymers of different compositions were studied, and their thermal decomposition behavior was compared to the corresponding homopolymers. The activation energies of the thermal decomposition were calculated using the Ozawa-Flynn-Wall, the Kissinger, and the Kissinger-Akahira-Sunose methodologies. The effects of the nature of the methacrylate monomer, the copolymer composition, and the rate of heating are discussed.

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Statistical copolymerization of N-vinyl-pyrrolidone and alkyl methacrylates via RAFT: reactivity ratios and thermal analysis

Cited by 14 publications

References 49 publications

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

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

Reactivity Ratios Estimation of the Free‐Radical Polymerization of Itaconic Acid and N‐Vinyl‐2‐Pyrrolidone by the Error‐in‐Variables Methodology

Thermal Stability and Kinetics of Thermal Decomposition of Statistical Copolymers of N-Vinylpyrrolidone and Alkyl Methacrylates Synthesized via RAFT Polymerization

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