Radiochemical studies of free-radical vinyl polymerizations: 7. Polymerization of methyl acrylate

Ayrey, G.; Humphrey, Michael; Poller, R. C.

doi:10.1016/0032-3861(77)90192-6

Cited by 29 publications

(17 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The presence of intermolecular chain transfer to polymer followed by termination by combination is the only explanation for the gel formation observed in the radical homopolymerization of acrylates. [20][21][22] Long-chain branching can lead to incomplete separation by SEC in terms of molecular weights: this has been shown to be theoretically possible [23,24] and confirmed experimentally for polyacrylates obtained using various radical polymerization processes. [25] Comparison of different multiple-detection SEC methods for the determination of molecular weights (viscometry and light scattering) allows detection of long-chain branching in polyacrylates.…”

Section: Introductionmentioning

confidence: 89%

Transfer to Polymer and Long‐Chain Branching in PLP–SEC of Acrylates

Castignolles

2009

Macromol. Rapid Commun.

View full text Add to dashboard Cite

Pulsed laser polymerization (PLP) combined with size exclusion chromatography (SEC) is the method of choice for determining propagation rate coefficients. The influence of the long-chain branching in PLP-SEC is investigated using multiple-detection SEC and a recently developed method to detect long-chain branching [P. Castignolles, R. Grab, M. Parkinson, M. Wilhelm, M. Gaborieau, Polymer 2009, 50, 2373.] While little or no long-chain branching is detected in poly(n-butyl acrylate), the error in relevant molecular weights of poly(2-ethylhexyl acrylate) is large (30-100%) due to long-chain branching. Possible variations of propagation rate coefficient with alkyl groups in alkyl acrylates or with the solvent have to be reconsidered.

show abstract

Section: Introductionmentioning

confidence: 89%

Transfer to Polymer and Long‐Chain Branching in PLP–SEC of Acrylates

Castignolles

2009

Macromol. Rapid Commun.

View full text Add to dashboard Cite

show abstract

“…[35,36] However, recent preliminary results indicate that disproportionation could be significant even at low temperatures (À34 8C). [37] Consequently, the fraction of termination occurring by disproportionation (l ¼ k td /k t ) is chosen to equal 0.3.…”

Section: Considerations Of the Model With Intramolecular Chain Transfmentioning

confidence: 95%

Simulation of Molecular Weight Distributions Obtained by Pulsed Laser Polymerization (PLP): New Analytical Expressions Including Intramolecular Chain Transfer to the Polymer

Nikitin

Castignolles

Charleux

et al. 2003

Macro Theory & Simulations

View full text Add to dashboard Cite

A new approach for the simulation of PLP (pulsed laser polymerization) is presented. This approach allows one to obtain new analytical solutions for different polymerization schemes, including either chain transfer to the monomer or intramolecular chain transfer to the polymer. The first results of the simulation of PLP experiments on n‐butyl acrylate at 20 °C and ambient pressure are presented.MWDs simulated for PLP of n‐butyl acrylate, in bulk at 20 °C and ambient pressure using three models: the model with intramolecular chain transfer to the polymer (solid line), the model with chain transfer to monomer (dashed line), and the classical model (dotted line).imageMWDs simulated for PLP of n‐butyl acrylate, in bulk at 20 °C and ambient pressure using three models: the model with intramolecular chain transfer to the polymer (solid line), the model with chain transfer to monomer (dashed line), and the classical model (dotted line).

show abstract

“…Their result indicates that the fraction of disproportionation in the total radical termination is about 64%. Ayrey et al (1977) did similar work on MA. They used [ I4C] azoisobutyronitrile as the initiator.…”

Section: Simulation Of Methyl Acrylate Polymerizationmentioning

confidence: 78%

“…Rubio et al (1981) studied the polymerization of MA with the redox system TiCL3/NH20H in a hydrochloric/ aqueous phase, and they found that when the conversion was above 40%, the polydispersity index (PDI) was over 20, which is a strong indication that branching is present. Ayrey et al (1977) conducted polymerizations of MA in benzene up to different conversion levels. Strong evidence supporting the suspicion of branching was that the PDI increased markedly with the extent of the reaction.…”

Section: Simulation Of Methyl Acrylate Polymerizationmentioning

confidence: 99%