Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate

Idowu, Loretta A.; Hutchinson, Robin A.

doi:10.3390/polym11030487

Cited by 21 publications

(35 citation statements)

References 36 publications

(119 reference statements)

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“…Copolymer composition was determined from 1 H NMR analysis conducted with a Bruker 400 MHz spectrometer and DMSO‐d 6 as solvent. Peaks assignments for the ─O─CH 2 ─ protons for MEA [ 9 ] and the ─O─CH 2 ─ and ─OH signals for HEMA [ 19 ] in DMSO‐d 6 were taken from previous studies, with peak assignments indicated on the poly(MEA‐co‐HEMA) 1 H NMR spectrum shown in Figure S5 in the Appendix S1. Peaks arising from HEMA monomer were usually not observed in the NMR spectra after purification of the poly(MEA‐co‐HEMA) samples; however, when necessary, peak integrations were adjusted to account for its presence when determining

F_{MEA}

according to Equations () and ():

F_{MEA} = 1 - \frac{\int {italicOH|}_{4.8 italicppm}}{\frac{1}{2} ((), \int {OC H_{2}|}_{3.8 italicppm} + \int {OC H_{2}|}_{4.2 italicppm})}

F_{MEA} = 1 - \frac{\int {italicOH|}_{4.8 italicppm}}{\frac{1}{2} ((), \int {{italicOCH}_{2}|}_{3.4 italicppm} + {{italicOCH}_{2}|}_{3.7 italicppm})}

Equation () was used to determine

F_{MEA}

in this study, as occasionally the

\int {OC {normalH}_{2}|}_{3.4 ppm}

signal overlapped with the H 2 O (or HOD) peak of DMSO‐d 6 appearing at 3.3 ppm.…”

Section: Methodsmentioning

confidence: 99%

The effect of hydrogen bonding on the copolymerization kinetics of 2‐methoxyethyl acrylate with 2‐hydroxyethyl methacrylate in alcohol and aqueous solutions

Agboluaje

Hutchinson

2021

Can J Chem Eng

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The influence of alcohol and alcohol/water solutions on the radical copolymerization kinetics of 2‐hydroxyethyl methacrylate (HEMA) with 2‐methoxyethyl acrylate (MEA) is studied using pulsed‐laser‐polymerization coupled with size exclusion chromatography. It is found that MEA incorporation into the copolymer is increased in butanol, methanol (MeOH), and MeOH/H2O solutions relative to the bulk system. Copolymer composition can be represented for solvent levels ≥50 vol.% by a single pair of reactivity ratios (rHEMA = 2.39 ± 0.16, rMEA0.25em= 0.28 ± 0.02) that differ from those in bulk (rHEMA = 3.14 ± 0.44, rMEA0.25em= 0.27 ± 0.04). MeOH as solvent slightly reduces the propagation rate coefficient ()kp of HEMA compared to the bulk system, in contrast to the increase in the MEA kp value. Thus, the value of kpcop is higher in MeOH for MEA‐rich systems compared to bulk, with the effect of the solvent reduced as the HEMA content in the comonomer mixture is increased. Adding water as cosolvent significantly increases kp values for both monomers, with kpcop in MeOH/H2O higher than bulk values over the complete composition range. Furthermore, kpcop for 50% monomer in the solvent systems studied can be represented by the implicit penultimate unit model using a single pair of radical reactivity ratios. It is concluded that the strongest influence of hydrogen‐bonding solvents compared to bulk is on the homopropagation kp values, rather than on copolymerization parameters, and that the difference in relative reactivity of non‐functional and functional monomers in bulk and aqueous solution should be accounted for when studying emulsion copolymerization.

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F_{MEA}

according to Equations () and ():

F_{MEA} = 1 - \frac{\int {italicOH|}_{4.8 italicppm}}{\frac{1}{2} ((), \int {OC H_{2}|}_{3.8 italicppm} + \int {OC H_{2}|}_{4.2 italicppm})}

F_{MEA} = 1 - \frac{\int {italicOH|}_{4.8 italicppm}}{\frac{1}{2} ((), \int {{italicOCH}_{2}|}_{3.4 italicppm} + {{italicOCH}_{2}|}_{3.7 italicppm})}

Equation () was used to determine

F_{MEA}

in this study, as occasionally the

\int {OC {normalH}_{2}|}_{3.4 ppm}

signal overlapped with the H 2 O (or HOD) peak of DMSO‐d 6 appearing at 3.3 ppm.…”

Section: Methodsmentioning

confidence: 99%

The effect of hydrogen bonding on the copolymerization kinetics of 2‐methoxyethyl acrylate with 2‐hydroxyethyl methacrylate in alcohol and aqueous solutions

Agboluaje

Hutchinson

2021

Can J Chem Eng

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“…By selecting the appropriate solvent, it is possible to break the intermolecular hydrogen bonds which result in a decrease in HEMA reactivity or introduce competitive hydrogen bonds what results in increase in HEMA reactivity. 39 Choosing the right solvent for copolymerization of HEMA allows to control the distribution of units in the copolymer chain. 39,40 The impact of hydrogen bonds on the solubility of PHEMA in water was described by Weaver et al 36 The authors observed that at a degree of polymerization below 30, PHEMA was soluble in water at any temperature.…”

Section: Introductionmentioning

confidence: 99%

“…39 Choosing the right solvent for copolymerization of HEMA allows to control the distribution of units in the copolymer chain. 39,40 The impact of hydrogen bonds on the solubility of PHEMA in water was described by Weaver et al 36 The authors observed that at a degree of polymerization below 30, PHEMA was soluble in water at any temperature. For degrees of polymerization in the range of 30-45, PHEMA was thermoresponsive in water.…”

Section: Introductionmentioning

confidence: 99%

Thermoresponsive P(HEMA-co-OEGMA) copolymers: synthesis, characteristics and solution behavior

et al. 2019

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“…Currently, acceptably accurate propagation rate coefficients have been reported for the monomers: styrene, methyl acrylate, butyl acrylate, ethyl acrylate, hydroxyethyl acrylate, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, vinylidene fluoride, hexafluoropropylene, and tetrafluorethylene [ 200 , 201 , 204 , 205 , 206 , 207 , 208 , 209 , 210 , 211 , 212 , 213 , 214 , 215 ].…”

Section: Case Studies For Connection Of Computational Chemistry and Kinetic Modelingmentioning

confidence: 99%

Connecting Gas-Phase Computational Chemistry to Condensed Phase Kinetic Modeling: The State-of-the-Art

et al. 2021

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In recent decades, quantum chemical calculations (QCC) have increased in accuracy, not only providing the ranking of chemical reactivities and energy barriers (e.g., for optimal selectivities) but also delivering more reliable equilibrium and (intrinsic/chemical) rate coefficients. This increased reliability of kinetic parameters is relevant to support the predictive character of kinetic modeling studies that are addressing actual concentration changes during chemical processes, taking into account competitive reactions and mixing heterogeneities. In the present contribution, guidelines are formulated on how to bridge the fields of computational chemistry and chemical kinetics. It is explained how condensed phase systems can be described based on conventional gas phase computational chemistry calculations. Case studies are included on polymerization kinetics, considering free and controlled radical polymerization, ionic polymerization, and polymer degradation. It is also illustrated how QCC can be directly linked to material properties.

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Solvent Effects on Radical Copolymerization Kinetics of 2-Hydroxyethyl Methacrylate and Butyl Methacrylate

Cited by 21 publications

References 36 publications

The effect of hydrogen bonding on the copolymerization kinetics of 2‐methoxyethyl acrylate with 2‐hydroxyethyl methacrylate in alcohol and aqueous solutions

The effect of hydrogen bonding on the copolymerization kinetics of 2‐methoxyethyl acrylate with 2‐hydroxyethyl methacrylate in alcohol and aqueous solutions

Thermoresponsive P(HEMA-co-OEGMA) copolymers: synthesis, characteristics and solution behavior

Connecting Gas-Phase Computational Chemistry to Condensed Phase Kinetic Modeling: The State-of-the-Art

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