Effect of Hydrogen Bonding on the Copolymerization of Styrene with Methacrylic Acid

ノグチ, アキヒロ; Kuzuya, Masayuki

doi:10.1002/1521-3935(20010401)202:7<1021::aid-macp1021>3.0.co;2-e

Cited by 6 publications

(11 citation statements)

References 17 publications

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“…However, the HEA levels in the unreacted comonomer mixture are significantly decreased from the feed composition. This result can be related to two phenomena; depropagation of methacrylate radicals and promotion of HEA incorporation through H‐bonding . Small‐scale PLP reactivity ratios suggest that f HEA ≈ F HEA for low HEA content comonomer mixtures in ketones, such that the experimental data should be overlapping with the feed composition.…”

Section: Resultsmentioning

confidence: 96%

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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Section: Resultsmentioning

confidence: 96%

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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“…The reason behind the higher kp cop for BA/HEA in xylenes is unclear, as a similar increase (relative to bulk behaviour) was not seen for BMA/HEA. 27 As hypothesized by Noguchi and Kuzuya, 26 perhaps the association between free polar monomer and recently polymerized units near the radical chain end leads to increased incorporation of the polar monomer, especially under diluted conditions in non-polar solvents, and thus the observed increase in kp cop in the acrylate only system. In contrast, kp cop in the methacrylate/acrylate system is largely controlled by the methacrylate (BMA) radical and thus is less affected by the H-bonding of the system.…”

mentioning

confidence: 81%

“…8 This important finding indicates that the influence of monomer induced H-bonding on copolymerization is of similar magnitude for acrylate and methacrylate only systems. However, it is not clear why the HEA (or HEMA) hydroxyl functionality does not also promote the reactivity of the BA (or BMA) in the bulk system; this behaviour may be related to hydrogen bonding between HEA monomer and units incorporated in the chain, an idea put forth by Noguchi and Kuzuya 26 and currently under further investigation. The previous methacrylate study also investigated the influence of solvent on the copolymerization parameters, finding that the additional H-bonding introduced through the addition of BuOH equalized the relative reactivity of HEMA and BMA such that the copolymer composition curve shifted to the diagonal.…”

Section: Ba/hea Copolymerization Kineticsmentioning

confidence: 99%

“…4 In an investigation of the solution copolymerization of styrene (ST) and MAA, however, it was hypothesized that interaction between MAA monomer and an incorporated MAA unit in the polymer backbone can channel MAA towards the propagating radical, leading to an increased incorporation into the copolymer, with the effect on MAA relative reactivity more pronounced under dilute conditions. 26 We have recently published results from a kinetic investigation of 2-hydroxyethyl acrylate (HEA), copolymerized with butyl methacrylate (BMA) in various organic solvents. 27 The presence of H-bonding introduced through the hydroxyl function of HEA affected the relative monomer reactivity, leading to an increased incorporation of HEA into the copolymer in a bulk system in comparison to butyl acrylate (BA) copolymerized with BMA.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen bonding in radical solution copolymerization kinetics of acrylates and methacrylates: a comparison of hydroxy- and methoxy-functionality

2017

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“…For example, Noguchi and Kuzuya substantiated through experiment and simulation that enhanced methacrylic acid (MAA) incorporation in MAA/ST copolymerization in dilute benzene solution could be represented by an intrachain reaction of chain-end radical with MAA monomers hydrogenbonded to MAA repeat units in the macroradical. 61 Therefore, future copolymerization investigations of hydroxyl-bearing (meth)acrylates, such as HEMA, could benefit from analogous consideration of monomer association to explain their peculiar trends in copolymer composition. Finally, the composition drifts are reorganized in Figure 7 to illustrate the macromonomer structure/reactivity relationship in solution copolymerization with ST.…”

Section: H Nmr)mentioning

confidence: 99%

Polyester Macromonomer Syntheses and Radical Copolymerization Kinetics with Styrene

2017

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Short-chain polyester methacrylate macromonomers with alkyl, tertiary amine, carboxyl, and hydroxyl end-group functionalities are synthesized by ring-opening polymerization and subsequent modification. Monomer conversion and composition drift during batch radical copolymerizations of (macro)monomer with styrene are tracked using the in situ NMR technique in both polar and nonpolar deuterated solvents at 80 °C. For experiments with initial methacrylate molar fraction f xMA = 0.2, the effects of end-group functionality, solvent, and hydrogen bonding on relative reactivity are pronounced for monomeric analogues of the macromonomers. However, the polyester spacers significantly dilute these effects in macromonomer copolymerization, as polyester type, length, and end-group functionality did not influence copolymerization kinetics. Instead, the chemical identity up to several units from the methacryloyl group is the most important indicator of macromonomer relative reactivity.

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Effect of Hydrogen Bonding on the Copolymerization of Styrene with Methacrylic Acid

Cited by 6 publications

References 17 publications

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

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

Hydrogen bonding in radical solution copolymerization kinetics of acrylates and methacrylates: a comparison of hydroxy- and methoxy-functionality

Polyester Macromonomer Syntheses and Radical Copolymerization Kinetics with Styrene

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