Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

Rintoul, Ignacio; Wandrey, Christine

doi:10.1016/j.polymer.2005.04.005

Cited by 61 publications

(101 citation statements)

References 15 publications

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“…However the reactivity ratios of charged monomers depend strongly on the pH and less strongly on the total ionic strength of the solution. [20,39,40] In general, the reactivity of a monomer decreases as it becomes ionized. This behavior can be understood as a result of the electrostatic repulsion between the ionic monomer and the charged polymer coil.…”

Section: Resultsmentioning

confidence: 99%

Online Monitoring of 4‐Vinylbenzene sulfonic acid Sodium Salt – Acrylamide Copolymerization in Water

Parıl

Alb

Giz

et al. 2009

Macromolecular Symposia

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Summary: 4-Vinylbenzene sulfonic acid sodium salt (VB) -Acrylamide (Aam) homopolymerization and copolymerization reactions with various feed ratios were performed in water at 60 8C. All reactions were monitored online, by an Automatic Continuous Online Monitoring of Polymerization (ACOMP) system. The concentrations of the two comonomers in their monomeric form, as well as their concentrations incorporated into polymer, were obtained from the monitored data. It was seen that Aam homopolymerization was faster than VB and both homopolymerization rates were higher than copolymerization rates at any combination. In the reactions with 1.5%, 5% and 10% (mol) VB, VB was completely depleted and further reaction was Aam homopolymerization. In the copolymerizations with 5 to 50% initial VB content, the plots of VB fraction in the remaining monomer mixture versus conversion exhibited a corner at 10-30% conversion. This corner showed that the behavior of the reaction changed abruptly at this point. In the first stage of the reactions, the composition was seen to be almost constant with almost no composition drift whereas in the second part, the VB fraction decreased monotonically. Monomer reactivity ratios (MRR) were calculated by error in variables (EVM) method. Since the reactions gave two distinguishable regions, the reaction part before and after the corner were evaluated separately. Therefore, the monomer reactivity ratios were found as r Aam ¼ 0.34 AE 0.07, r VB ¼ 0.40 AE 0.21 for the part before and r Aam ¼ 0.2 AE 0.04, r VB ¼ 9.0 AE 0.8 for the part after the corner.

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Section: Resultsmentioning

confidence: 99%

Online Monitoring of 4‐Vinylbenzene sulfonic acid Sodium Salt – Acrylamide Copolymerization in Water

Parıl

Alb

Giz

et al. 2009

Macromolecular Symposia

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“…Therefore, mathematical modelling for radical copolymerization of acrylic acid-acrylamide monomers with monofunctional initiator (APS) and crosslinker (NMBA) was simulated by Monte-Carlo method in order to interpret the product distributions of polymerization reactions [23,24]. The reactivity ratios for acrylic acid and acrylamide monomers were equivalent to r 1 = 0.3234 and r 2 = 2.0066, respectively [25]. Moreover, the concentrations of active carboxylic (-COOH) and amide (-CONH 2 ) groups within various hydrogel matrices were measured volumetrically [26,27].…”

Section: Microstructural Analysismentioning

confidence: 99%

“…Fig. 3 B and C. Depending on the relative reactivity ratios characterized for acrylic acid and acrylamide monomers [25], the AA-co-AM-20 possesses limited polymeric chain length of almost single acrylamide co-monomer sequence (Fig. 3 C).…”

Section: Microstructural Propertiesmentioning

confidence: 99%

Does poly(acrylic acid-co-acrylamide) hydrogel be the pluperfect choiceness in treatment of dyeing wastewater? “From simple copolymer to gigantic aqua-waste remover”

Mekewi

Madkour

Darwish

et al. 2015

Journal of Industrial and Engineering Chemistry

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“…The most recent studies on the effect of charge interactions on the kinetics of water-soluble, ionized, or ionizable monomers have been largely focused on copolymer composition: in this way, it is possible to isolate the contribution of propagation reactions and specifically address the sensitivity of propagation reactivity ratios upon changes in ionic strength, monomer concentration and ionization, pH, etc. [10,11,15,16]. On the other hand, the investigation of such effects on the polymerization rate is of great interest due to its implications on the final polymer properties (e.g., molar masses).…”

Section: Introductionmentioning

confidence: 99%

Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid

2017

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Water-soluble, carboxylic acid monomers are known to exhibit peculiar kinetics when polymerized in aqueous solution. Namely, their free-radical polymerization rate is affected by several parameters such as monomer concentration, ionic strength, and pH. Focusing on methacrylic acid (MAA), even though this monomer has been largely addressed, a systematic investigation of the effects of the above-mentioned parameters on its polymerization rate is missing, in particular in the fully ionized case. In this work, the kinetics of non-ionized and fully ionized MAA are characterized by in-situ nuclear magnetic resonance (NMR). Such accurate monitoring of the reaction rate enables the identification of relevant but substantially different effects of the monomer and electrolyte concentration on polymerization rate in the two ionization cases. For non-ionized MAA, the development of a kinetic model based on literature rate coefficients allows us to nicely simulate the experimental data of conversion versus time at a high monomer concentration. For fully ionized MAA, a novel propagation rate law accounting for the electrostatic interactions is proposed: the corresponding model is capable of predicting reasonably well the electrolyte concentration effect on polymerization rate. Nevertheless, further kinetic information in a wider range of monomer concentrations would be welcome to increase the reliability of the model predictions.

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Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

Cited by 61 publications

References 15 publications

Online Monitoring of 4‐Vinylbenzene sulfonic acid Sodium Salt – Acrylamide Copolymerization in Water

Online Monitoring of 4‐Vinylbenzene sulfonic acid Sodium Salt – Acrylamide Copolymerization in Water

Does poly(acrylic acid-co-acrylamide) hydrogel be the pluperfect choiceness in treatment of dyeing wastewater? “From simple copolymer to gigantic aqua-waste remover”

Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid

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