Chain Transfer to Monomer and Polymer in the Radical Polymerization of Vinyl Neo-decanoate

Robert Balic; Christopher M. Fellows; Alex M. van Herk

Macromolecular Research, Vol.12, No.4, 325-335, August, 2004

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Chain Transfer to Monomer and Polymer in the Radical Polymerization of Vinyl Neo-decanoate

Robert Balic^{1, †}, Christopher M. Fellows^{1, 2}, and Alex M. van Herk³

¹Key Centre for Polymer Colloids, School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia
²School of Biological, Biomedical, and Molecular Sciences, University of New England, Armidale, NSW 2351, Australia
³Department of Polymer Chemistry and Technology, Eindhoven University of Technology, P.O. Box 513, MB 5600 MB Eindhoven, Netherlands

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Molecular weight distributions of poly(vinyl neo-decanoate) produced by the bulk polymerization of the monomer to low conversions were investigated to obtain values of the rate constants for the chain transfer to monomer (C_M). The value of C_M of 7.5 (± 0.6) × 10^-4 was obtained from a logarithmic plot of the number distribution at 5, 25, and 50 ℃, which suggests that the activation energy for chain transfer is on the order of 20-25 kJ mol^-1. These plots were linear between the number and weight-average degrees of polymerization, but not over the whole molecular weight range for which a significant signal was observed in the gel permeation chromatography (GPC) trace. Modeling suggests that the deviations observed at high molecular weights can be explained by branching of the chains through chain transfer to the polymer, with a branching density as low as 10_-5, without affecting the slope at low values of the number of monomer unit, N. This deviation from the expected distribution of linear chains was used to estimate the branching densities at low conversion.

Keywords:chain transfer to monomer;chain transfer to polymer;vinyl neo-decanoate;size exclusion chromatography;free-radical polymerisation.

[References]

Buselli AJ, Lindemann MK, Blades CE, J. Polym. Chem., 28, 485 (1958)
Brandrup J, Immergut EH, Grulke EA, Eds., Polymer Handbook, John Wiley & Sons, New York (1999)
Clay PA, Gilbert RG, Macromolecules, 28(2), 552 (1995)
Moad G, Moad CL, Macromolecules, 29(24), 7727 (1996)
Heuts JPA, Davis TP, Russell GT, Macromolecules, 32(19), 6019 (1999)
Balic R, Gilbert RG, Zammit MD, Davis TP, Miller CM, Macromolecules, 30(13), 3775 (1997)
Hutchinson RA, Paquet DA, McMinn JH, Beuermann S, Fuller RE, Jackson C, Dechema Monographs, 131, 467 (1995)
Shortt DW, J. Liquid Chromat., 16, 3371 (1993)
Maeder S, Gilbert RG, Macromolecules, 31(14), 4410 (1998)
Sangster DF, Feldthusen J, Strauch J, Steng M, Fellows CM, Gilbert RG, to be submitted 2004
Cunningham MF, Geramita K, Ma JW, Polymer, 41(14), 5385 (2000)
De Bruyn H, PhD Thesis, Sydney University, Sydney (1998)
Scholten H, Vermeulen J, Westrenen V, Polym. Paint Colour J., 178, 852 (1988)
Scholten H, Reader C, First Asia-Pacific Conference on Advances in Coatings Technology, Singapore (1991)
Subramaniam N, PhD Thesis, University of Sydney, Sydney (1999)
Kerr JA, Ed., Rate Processes in the Gas Phase, Wiley Interscience, New York (1973)
Hutchinson RA, Richards JR, Aronson MT, Macromolecules, 27(16), 4530 (1994)
Stickler M, Meyerhoff G, Makromol. Chem., 179, 2729 (1978)
Clay PA, Gilbert RG, Russell GT, Macromolecules, 30(7), 1935 (1997)
Ghielmi A, Fiorentino S, Storti G, Mazzotti M, Morbidelli M, J. Polym. Sci. A: Polym. Chem., 35(5), 827 (1997)
Thomas S, Hamielec A, Soares J, Polym. React. Eng., 5(4), 183 (1997)
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Sayer C, Araujo PHH, Arzamendi G, Asua JM, Lima EL, Pinto JC, J. Polym. Sci. A: Polym. Chem., 39(20), 3513 (2001)
Tobita H, J. Polym. Sci. B: Polym. Phys., 39(4), 391 (2001)
Tobita H, Polymer, 35(14), 3023 (1994)
Tobita H, Acta Polym., 46, 185 (1995)
Flory PJ, Principles of Polymer Chemistry, Cornell University Press Ithaca (1953)
Ahmad NM, Heatley F, Lovell PA, Macromolecules, 31(9), 2822 (1998)
Hamielec AE, in Synthesis, Kinetics, and Characterization of Poly(vinyl acetate), M. S. El-Aasser and J. W. Vanderhoff, Eds., Applied Science Publishers, London (1981)
Britton D, Heatley F, Lovell PA, Macromolecules, 31(9), 2828 (1998)
Graessley WW, Hartung RD, Uy WC, J. Polym. Sci, A2, 1919 (1969)
Billmeyer FW, Textbook of Polymer Science, Wiley-Interscience, New York (1962)

[Referenced By]

[1] Buselli AJ, Lindemann MK, Blades CE, J. Polym. Chem., 28, 485 (1958)

[2] Brandrup J, Immergut EH, Grulke EA, Eds., Polymer Handbook, John Wiley & Sons, New York (1999)

[3] Clay PA, Gilbert RG, Macromolecules, 28(2), 552 (1995)

[4] Moad G, Moad CL, Macromolecules, 29(24), 7727 (1996)

[5] Heuts JPA, Davis TP, Russell GT, Macromolecules, 32(19), 6019 (1999)

[6] Balic R, Gilbert RG, Zammit MD, Davis TP, Miller CM, Macromolecules, 30(13), 3775 (1997)

[7] Hutchinson RA, Paquet DA, McMinn JH, Beuermann S, Fuller RE, Jackson C, Dechema Monographs, 131, 467 (1995)

[8] Shortt DW, J. Liquid Chromat., 16, 3371 (1993)

[9] Maeder S, Gilbert RG, Macromolecules, 31(14), 4410 (1998)

[10] Sangster DF, Feldthusen J, Strauch J, Steng M, Fellows CM, Gilbert RG, to be submitted 2004

[11] Cunningham MF, Geramita K, Ma JW, Polymer, 41(14), 5385 (2000)

[12] De Bruyn H, PhD Thesis, Sydney University, Sydney (1998)

[13] Scholten H, Vermeulen J, Westrenen V, Polym. Paint Colour J., 178, 852 (1988)

[14] Scholten H, Reader C, First Asia-Pacific Conference on Advances in Coatings Technology, Singapore (1991)

[15] Subramaniam N, PhD Thesis, University of Sydney, Sydney (1999)

[16] Kerr JA, Ed., Rate Processes in the Gas Phase, Wiley Interscience, New York (1973)

[17] Hutchinson RA, Richards JR, Aronson MT, Macromolecules, 27(16), 4530 (1994)

[18] Stickler M, Meyerhoff G, Makromol. Chem., 179, 2729 (1978)

[19] Clay PA, Gilbert RG, Russell GT, Macromolecules, 30(7), 1935 (1997)

[20] Ghielmi A, Fiorentino S, Storti G, Mazzotti M, Morbidelli M, J. Polym. Sci. A: Polym. Chem., 35(5), 827 (1997)

[21] Thomas S, Hamielec A, Soares J, Polym. React. Eng., 5(4), 183 (1997)

[22] Bamford CH, Tompa H, J. Polym. Sci., 10, 345 (1952)

[23] Sayer C, Araujo PHH, Arzamendi G, Asua JM, Lima EL, Pinto JC, J. Polym. Sci. A: Polym. Chem., 39(20), 3513 (2001)

[24] Tobita H, J. Polym. Sci. B: Polym. Phys., 39(4), 391 (2001)

[25] Tobita H, Polymer, 35(14), 3023 (1994)

[26] Tobita H, Acta Polym., 46, 185 (1995)

[27] Flory PJ, Principles of Polymer Chemistry, Cornell University Press Ithaca (1953)

[28] Ahmad NM, Heatley F, Lovell PA, Macromolecules, 31(9), 2822 (1998)

[29] Hamielec AE, in Synthesis, Kinetics, and Characterization of Poly(vinyl acetate), M. S. El-Aasser and J. W. Vanderhoff, Eds., Applied Science Publishers, London (1981)

[30] Britton D, Heatley F, Lovell PA, Macromolecules, 31(9), 2828 (1998)

[31] Graessley WW, Hartung RD, Uy WC, J. Polym. Sci, A2, 1919 (1969)

[32] Billmeyer FW, Textbook of Polymer Science, Wiley-Interscience, New York (1962)