Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

Daria E. Lonsdale; Geoffrey Johnston-Hall; Amanda Fawcett; Craig A. Bell; Carl N. Urbani; Michael R. Whittaker; Michael J. Monteiro

doi:10.1002/pola.22101

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

Daria E. Lonsdale, Geoffrey Johnston-Hall, Amanda Fawcett, Craig A. Bell, Carl N. Urbani, Michael R. Whittaker, Michael J. Monteiro

Research output: Contribution to journal › Article › Research › peer-review

11 Citations (Scopus)

Abstract

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^-3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^-3). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism.

Original language	English
Pages (from-to)	3620-3625
Number of pages	6
Journal	Journal of Polymer Science, Part A: Polymer Chemistry
Volume	45
Issue number	16
DOIs	https://doi.org/10.1002/pola.22101
Publication status	Published - 15 Aug 2007
Externally published	Yes

Keywords

Kinetics (polym.)
Modeling
Radical polymerization
Retardation time

Access to Document

10.1002/pola.22101

Cite this

@article{8b8576ef469140269a042626cdb76e18,

title = "Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent",

abstract = "In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10-3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10-3). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism.",

keywords = "Kinetics (polym.), Modeling, Radical polymerization, Retardation time",

author = "Lonsdale, {Daria E.} and Geoffrey Johnston-Hall and Amanda Fawcett and Bell, {Craig A.} and Urbani, {Carl N.} and Whittaker, {Michael R.} and Monteiro, {Michael J.}",

year = "2007",

month = aug,

day = "15",

doi = "10.1002/pola.22101",

language = "English",

volume = "45",

pages = "3620--3625",

journal = "Journal of Polymer Science, Part A: Polymer Chemistry",

issn = "0887-624X",

publisher = "John Wiley & Sons",

number = "16",

}

TY - JOUR

T1 - Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

AU - Lonsdale, Daria E.

AU - Johnston-Hall, Geoffrey

AU - Fawcett, Amanda

AU - Bell, Craig A.

AU - Urbani, Carl N.

AU - Whittaker, Michael R.

AU - Monteiro, Michael J.

PY - 2007/8/15

Y1 - 2007/8/15

N2 - In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10-3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10-3). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism.

AB - In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (Ctrs) determined using the Mayo method is equal to 3.8 × 10-3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10-3). Simulations, including chain-length-dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion-time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the Mn data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism.

KW - Kinetics (polym.)

KW - Modeling

KW - Radical polymerization

KW - Retardation time

UR - http://www.scopus.com/inward/record.url?scp=34548185194&partnerID=8YFLogxK

U2 - 10.1002/pola.22101

DO - 10.1002/pola.22101

M3 - Article

AN - SCOPUS:34548185194

VL - 45

SP - 3620

EP - 3625

JO - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

SN - 0887-624X

IS - 16

ER -

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

Abstract

Keywords

Access to Document

Other files and links

Cite this