High‐conversion catalytic chain transfer polymerization of methyl methacrylate

Pierik, Sebastiaan C. J.; Herk, Alex M. van

doi:10.1002/app.13020

Cited by 14 publications

(15 citation statements)

References 41 publications

(70 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Therefore, copolymerization with BA is expected to occur as well. Finally, cobalt(II) catalyst deactivation, as discussed in a previous paper32 for the CCT homopolymerization of MMA, is likely to occur in the copolymerization as well.…”

Section: Resultsmentioning

confidence: 85%

“…Square, solid line: expected to occur as well. Finally, cobalt(II) catalyst deactivation, as discussed in a previous paper [32] for the CCT homopolymerization of MMA, is likely to occur in the copolymerization as well. Two high conversion CCT copolymerizations of MMA and BA were performed to investigate which of the above effects are of importance.…”

Section: Effect Of Conversion On Cct Copolymerization Of Mma and Bamentioning

confidence: 99%

“…In addition, cobalt(II) deactivation may take place, as discussed before. [32] The differences in molecular weight between both experiments stem from Figure 11. Evolution of MWDs with conversion for the CCT copolymerization of MMA and BA in toluene at 60 8C.…”

Section: Effect Of Conversion On Cct Copolymerization Of Mma and Bamentioning

confidence: 99%

“…Unless otherwise stated simulations are run in moments mode. The standard set of reactions taken into account in the simulations has been reported previously 32. An overview of all reactions and rate coefficients is available through the Supporting Information .…”

Section: Experimental Partmentioning

confidence: 99%

See 3 more Smart Citations

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Pierik

Herk

2003

Macro Chemistry & Physics

View full text Add to dashboard Cite

In this work it is shown that catalytic chain transfer is a very efficient way of controlling molecular weight in the copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The experimental data are compared to a previously developed model based on copolymerization kinetics and the mechanisms for catalytic chain transfer and for cobalt‐mediated living radical polymerization that can describe the observed transfer constants. Secondly, it is shown that the presence of a catalytic chain transfer agent does not affect the reactivity ratios within the concentration range studied. Finally, the effect of conversion and therewith composition drift on the catalytic chain transfer polymerization of MMA and BA is investigated and it is shown that under the conditions employed in the experiments a certain degree of macromer copolymerization is present at high partial conversions of MMA.

show abstract

Section: Resultsmentioning

confidence: 85%

Section: Effect Of Conversion On Cct Copolymerization Of Mma and Bamentioning

confidence: 99%

Section: Effect Of Conversion On Cct Copolymerization Of Mma and Bamentioning

confidence: 99%

Section: Experimental Partmentioning

confidence: 99%

See 2 more Smart Citations

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Pierik

Herk

2003

Macro Chemistry & Physics

View full text Add to dashboard Cite

show abstract

“…However, in polymerizations up to high conversion, catalyst deactivation in the presence of acetic acid and benzoyl peroxide is observed, indicating that the effects of deactivation become apparent only at longer timescales. [40] As alcohols are present in alkyl esters, methanol was tested as well, but it did not change the obtained transfer coefficients, and neither did 1-dodecanethiol. Only in THF did C T decrease quite drastically, but only at concentrations of THF over 1 mol Á L À1 .…”

Section: Purified Solventmentioning

confidence: 99%

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Pierik¹,

Vollmerhaus²,

Herk³

2003

Macro Chemistry & Physics

View full text Add to dashboard Cite

In the catalytic chain transfer polymerization of methyl methacrylate, butyl methacrylate and 2‐ethylhexyl methacrylate in toluene, it was found that the chain transfer constants (CT) were independent of solvent concentration and therefore of solution viscosity, and did not differ from the bulk polymerization values. For a diffusion controlled system, theoretical calculations predict an increase in CT when the solution viscosity is lowered. This points at a non‐diffusion controlled catalytic chain transfer step. These results were obtained when the solvent was thoroughly purified using a Grubbs‐type set‐up, whereas a large reduction in CT was found in unpurified solvent. Similar results were obtained for butyl acetate. Therefore it is concluded that the decrease of CT in non‐purified solvents is not related to the solvent itself, but to solvent impurities. Further we found that methyl methacrylate ended radicals do not covalently bind to the cobalt complex, in contrast to styrene and acrylate ended radicals.Chain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.magnified imageChain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.

show abstract

Molecular Weight Control in Emulsion Polymerization by Catalytic Chain Transfer: A Reaction Engineering Approach

Smeets

Meda

Heuts

et al. 2007

Macromolecular Symposia

View full text Add to dashboard Cite

Summary: For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on the Mayo equation, catalyst partitioning and deactivation was developed. The influence of several reaction parameters on the instantaneous number average molecular weight was quantified.

show abstract

High‐conversion catalytic chain transfer polymerization of methyl methacrylate

Cited by 14 publications

References 41 publications

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Molecular Weight Control in Emulsion Polymerization by Catalytic Chain Transfer: A Reaction Engineering Approach

Contact Info

Product

Resources

About