Measurement of Transfer Coefficients to Monomer for <i>n</i>‐Butyl Methacrylate by Molecular Weight Distributions from Emulsion Polymerization

Sangster, David F.; Feldthusen, Jesper; Strauch, Jelica; Fellows, Christopher M.

doi:10.1002/macp.200800059

Cited by 24 publications

(19 citation statements)

References 56 publications

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“…The desorption coefficient of a monomeric radical is given by eq . Assuming a particle diameter of 100 nm, a partition coefficient

M

of 7 × 10 7

{normalm}_{aq}^{3}

{normalm}_{mon,}^{3}

an aqueous phase diffusion coefficient of 1.2 × 10 −9 m 2 /s and a chain transfer coefficient (to monomer) equal to the chain transfer coefficient of butyl methacrylate (i.e., 2 × 10 −5 m 3 /(mol s)], the time constant for desorption of monomeric radicals is 3.3 × 10 7 s …”

Section: Resultsmentioning

confidence: 99%

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

Jansen

Meuldijk

Lovell

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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Successful miniemulsion polymerizations of very hydrophobic monomers, such as lauryl methacrylate and 4-tertbutyl styrene, initiated by very hydrophobic (i.e., completely water-insoluble) lauroyl peroxide, are reported. Conversion-time histories, as well as final latex properties, for example, the particle size distribution, are different from similar miniemulsion polymerizations in the presence of water-soluble initiators. The observed differences can be attributed to the average number of radicals inside a miniemulsion particle; the system obeys Smith-Ewart case I rather than Case II kinetics. Albeit the pairwise generation of radicals in the monomer droplets, substantial polymerization rates are observed. Water, present in the droplet interfacial layer, is supposed to act as chain transfer agent. The product of a chain transfer event is a hydroxyl radical, exit of this hydroxyl radical allows for the presence of single radicals in particles. The proposed mechanisms allow for agreement between initial droplet and final particle size distributions in miniemulsion polymerization initiated by lauroyl peroxide.

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“…The desorption coefficient of a monomeric radical is given by eq . Assuming a particle diameter of 100 nm, a partition coefficient

M

of 7 × 10 7

{normalm}_{aq}^{3}

{normalm}_{mon,}^{3}

Section: Resultsmentioning

confidence: 99%

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

Jansen

Meuldijk

Lovell

et al. 2016

J. Polym. Sci. Part A: Polym. Chem.

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“…In Equation , S is the amount of emulsifier (g), V w the water volume (L), M we the emulsifier molar mass (g · mol −1 ), a s the emulsifier coverage area (Å 2 ), CMC the critical micellar concentration (mol · L −1 ), D p (cm) the particle diameter, and n agg the emulsifier aggregation number. The values of all the parameters used are listed in Table as well as the references from where the parameters were taken …”

Section: The Modelmentioning

confidence: 99%

Modeling the Semicontinuous Heterophase Polymerization for Synthesizing Poly(n‐butyl methacrylate) Nanoparticles

Pérez-García

Pérez-Carrillo

Mendizábal

et al. 2013

Macro Reaction Engineering

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A simple four-state model containing five-parameters, in conjunction with experimental conversion, particle number density and average molar masses, is presented to reproduce the semicontinuous heterophase polymerization of butyl methacrylate. The model adequately describes the experimental evolutions of conversion, particle size, average number of particles, average number of radicals per particle, and molar mass. A coagulation mechanism was detected and its rate constant was evaluated. The entry coefficient and the critical radical concentration in the aqueous phase were approximately constant and the exit rate coefficient decreased with monomer feed rate. Homogeneous nucleation is the dominant mechanism of production of particles, micellar nucleation occurs at the slowest feeding rate examined.

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“…Poly( n -butyl methacrylate) [poly(BMA)] was chosen as a second block because bis(initiator) 2 is soluble in the monomer, and the star block copolymer should exhibit two T g s; the glass-transition temperature of poly(BMA) is much lower ( T g ∼20 °C) than that of polystyrene with which it is immiscible. After polymerization for 3 days at 135 °C, the supramolecular four-arm star copolymer ( 4 ) was obtained by precipitations from chloroform and then from tetrahydrofuran (THF) into methanol; the SEC trace of the initial product contained a high molecular weight fraction (Figure ) believed to have arisen from initiation of BMA by a small amount of free, uncomplexed initiator 2 or chain transfer to monomer . The initial product was fractionated by addition of methanol to a solution of 1:1 dioxane:THF until it became slightly cloudy; filtration of the high molecular weight precipitate and evaporation of the filtrate yielded the final four-armed star polyrotaxane 4 .…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Four-Armed Star A₂B₂ Copolymer (Miktoarm Star) via Host–Guest Complexation and Nitroxide-Mediated Radical Polymerization

Lee

Gibson

2020

Macromolecules

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A supramolecular four-armed star copolymer was prepared from the pseudorotaxane complex of a crown-centered polystyrene and a bis(2,2,6,6-tetramethylpiperidinyl-1-oxy) viologen compound and n-butyl methacrylate (BMA) by nitroxide-mediated polymerization of the latter. Solvent fractionation with dioxane/THF/MeOH removed a small amount of a high molecular weight poly(BMA) homopolymer. The molecular weight increase from its monomodal size exclusion chromatographic trace gives direct evidence of the four-armed star copolymer formation; there is no residual starting polystyrene. NMR spectroscopy shows the two components of the copolymer and confirms the presence of the central [2]rotaxane unit. Differential scanning calorimetry displays two glass-transition temperatures, which correspond closely to those of polystyrene and poly(BMA).

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Measurement of Transfer Coefficients to Monomer for n‐Butyl Methacrylate by Molecular Weight Distributions from Emulsion Polymerization

Cited by 24 publications

References 56 publications

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

Modeling the Semicontinuous Heterophase Polymerization for Synthesizing Poly(n‐butyl methacrylate) Nanoparticles

Supramolecular Four-Armed Star A₂B₂ Copolymer (Miktoarm Star) via Host–Guest Complexation and Nitroxide-Mediated Radical Polymerization

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Measurement of Transfer Coefficients to Monomer for n‐Butyl Methacrylate by Molecular Weight Distributions from Emulsion Polymerization

Cited by 24 publications

References 56 publications

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics, kinetics, and mechanism

Modeling the Semicontinuous Heterophase Polymerization for Synthesizing Poly(n‐butyl methacrylate) Nanoparticles

Supramolecular Four-Armed Star A2B2 Copolymer (Miktoarm Star) via Host–Guest Complexation and Nitroxide-Mediated Radical Polymerization

Contact Info

Product

Resources

About

Supramolecular Four-Armed Star A₂B₂ Copolymer (Miktoarm Star) via Host–Guest Complexation and Nitroxide-Mediated Radical Polymerization