The influence of hydrogen bonding on radical chain-growth parameters for butyl methacrylate/2-hydroxyethyl acrylate solution copolymerization

Schier, Jan E. S.; Hutchinson, Robin A.

doi:10.1039/c6py00834h

Cited by 34 publications

(92 citation statements)

References 44 publications

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“…The values of E a found in the investigated temperature range for the various ILs and solution concentrations are rather similar (20–22 kJ mol −1 ) and also quite close to the to the value 22.4 kJ mol −1 reported in the IUPAC benchmark paper for pure MMA . Besides an influence of the ionic liquid concentration on the absolute homopropagation rate coefficients, also changes in copolymerization parameters have been reported.…”

Section: Introductionsupporting

confidence: 86%

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Deglmann

Hungenberg²,

Vale

2018

Macro Reaction Engineering

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Authors want to communicate that there is a typing error in the following sentence in paragraph 4.5:The largest medium effects of combinatorial origin are expected for systems with either (v S /v M ) >> 1, i.e., for large monomers such as iBoMA in small solvents like CO 2 , or systems with (v S /v M ) << 1, i.e., for the smallest monomer ethylene in large solvents like ILs.should read as follows:The largest medium effects of combinatorial origin are expected for systems with either (v S /v M ) << 1, i.e., for large monomers such as iBoMA in small solvents like CO 2 , or systems with (v S /v M ) >> 1, i.e., for the smallest monomer ethylene in large solvents like ILs.All presented results remain unchanged and correct; they are not affected by this oversight.

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Section: Introductionsupporting

confidence: 86%

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Deglmann

Hungenberg²,

Vale

2018

Macro Reaction Engineering

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“…At the end of reaction, the M w for the HEA copolymer is tripled (16 600 g mol −1 ) over the final value for the BA copolymer. Whereas some differences were expected due to the differences in reactivity ratios that favor HEA incorporation and the increase in k p cop , this very large change in polymer molar masses was surprising. Insight into the result can be obtained by examining the complete MMD of the poly(BMA/HEA) produced in xylenes, also shown in Figure .…”

Section: Resultsmentioning

confidence: 93%

“…However, the suitability of the model to represent copolymerization of monomers with hydroxyl functionality such as 2‐hydroxyethyl acrylate (HEA) or 2‐hydroxyethyl methacrylate (HEMA) needs to be carefully evaluated, as shown by a study of ST/HEMA kinetics in which the level of HEMA incorporated into the polymer was found to increase as the solvent was changed from polar dimethyl formamide to bulk to nonpolar toluene . More recently, the copolymerization of HEA with both BMA and BA has been systematically studied, with similar solvent‐dependent shifts in composition observed . In addition, the relative levels of solvent and free monomer have been shown to influence the rate of backbiting during HEA (co)polymerization, and a small amount of ethylene glycol dimethacrylate (EGDMA) impurity contained in HEMA was hypothesized to be the cause of a large increase in polymer MMs produced under semibatch conditions for ST/HEMA and BMA/HEMA, but not BA/HEMA …”

Section: Introductionmentioning

confidence: 99%

“…As hydrogen bonding can greatly affect copolymerization behavior of hydroxyfunctional monomers, and since HEA (and HEMA) are frequently used as reactive components in automotive coatings resins, it is necessary to validate whether the generalized modeling structure previously developed can be applied to represent BMA/HEA high temperature semibatch copolymerization, using the recently measured propagation kinetic coefficients determined by low conversion PLP experiments at lower temperatures in bulk and a variety of solvents . The BMA/HEA semibatch copolymerization behavior (i.e., free monomer profiles and polymer molar mass averages and distributions) is compared to that of the previously studied and modeled BMA/BA system .…”

Section: Introductionmentioning

confidence: 99%

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Modeling of Semibatch Solution Radical Copolymerization of Butyl Methacrylate and 2‐Hydroxyethyl Acrylate

Schier

Zhang

Grady

et al. 2018

Macro Reaction Engineering

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thermoset complex copolymers, a change driven by the need to maintain relatively low solution viscosity for efficient application of the coating while greatly reducing the solvent level in the formulation. [1][2][3] Control of both composition and chain length of these new materials is paramount to ensure that the reactive groups, introduced by utilizing (meth)acrylates with glycidyl, hydroxyl, and/or carboxylic acid functionality, are uniform across the chain distribution while specific target qualities (e.g., resin refractive index, glass transition temperature, solution viscosity) are maintained. [4,5] A generalized simulation framework provides a means to systematically capture the knowledge required to develop and efficiently maintain a diverse portfolio of products. Modeling strategies, such as the method of moments pioneered by Ray, [6] are required for the simultaneous modeling of copolymer composition and polymer MM averages during radical copolymerization. [7][8][9] Ray and co-workers combined the specialized modeling strategies required to represent polymer structure into a simulation package, POLYRED, [10,11] that was applied for the representation of solution, [7] suspension, [12] and emulsion [13] radical copolymerization, among other chemistries. The challenge is to develop a modeling platform that can capture the complexities of current recipes and be easily adapted and extended to include new monomers and reaction conditions.A firm knowledge of the basic set of radical polymerization mechanisms and the associated kinetic coefficients is required. The application of specialized experimental techniques has led to the understanding of "family-type" behavior; i.e., that all methacrylate monomers show generalized trends in rate coefficients that are distinctly different than those seen for acrylate monomers or styrene. Propagation kinetics, for example, of styrene, [14] alkyl and functional methacrylates, [15,16] and alkyl acrylates [17,18] are now well understood after application of the IUPAC recommended pulsed laser polymerization-size exclusion chromatography (PLP-SEC) technique. Understanding of radical termination kinetics has also been generalized, with knowledge gained from PLP techniques coupled with electron paramagnetic resonance (EPR) spectroscopy to monitor radical concentrations, as summarized in a recent update from Buback et al. [19] With knowledge of initiation, propagation, and termination kinetics, monomer consumption rates and associated heat releases can be calculated. Equally important, knowledge of the basic radical polymerization kinetics has led to better Semibatch CopolymerizationNonfunctional monomer feedstocks containing alkyl meth(acrylate) components such as butyl acrylate (BA) and butyl methacrylate (BMA) are replaced or augmented with functional monomers such as 2-hydroxyethyl methacrylate (HEMA) and 2-hydroxyethyl acrylate (HEA) to produce reactive polymer chains of lowered molar mass for application in solvent-borne automotive coatings. The introduction of such polar ...

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“…Although k p is dependent on monomer concentration, it was found that the reactivity ratios of AM and non-ionized acrylic acid copolymerization were constant with concentration [21], although the values are dependent on monomer concentration and ionic strength for copolymerization of AM with fully-ionized AA [22,23]. It should be noted that hydrogen-bonding effects are not only present in aqueous solution, but also influence the reactivity ratios of butyl methacrylate (BMA) and 2-hydroxyethyl acrylate (HEA) copolymerization in organic solution, as the relative reactivity of the two monomers is dependent on solvent choice [24].…”

Section: Introductionmentioning

confidence: 99%

Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

Luk

Hutchinson

2017

Processes

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Abstract:The radical copolymerization kinetics of acrylamide (AM) and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL), are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (k t ). The estimate for k t,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

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The influence of hydrogen bonding on radical chain-growth parameters for butyl methacrylate/2-hydroxyethyl acrylate solution copolymerization

Cited by 34 publications

References 44 publications

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Modeling of Semibatch Solution Radical Copolymerization of Butyl Methacrylate and 2‐Hydroxyethyl Acrylate

Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

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