Catalytic chain transfer for molecular weight control in the emulsion homo- and copolymerizations of methyl methacrylate and butyl methacrylate

Kukulj, Dax, Davis, Thomas P., Suddaby, Kevin G., Haddleton, David M. and Gilbert, Robert G. (1997) Catalytic chain transfer for molecular weight control in the emulsion homo- and copolymerizations of methyl methacrylate and butyl methacrylate. Journal of Polymer Science, Part A: Polymer Chemistry, 35 5: 859-878. doi:10.1002/(SICI)1099-0518(19970415)35:5<859::AID-POLA2>3.0.CO;2-G


Author Kukulj, Dax
Davis, Thomas P.
Suddaby, Kevin G.
Haddleton, David M.
Gilbert, Robert G.
Title Catalytic chain transfer for molecular weight control in the emulsion homo- and copolymerizations of methyl methacrylate and butyl methacrylate
Journal name Journal of Polymer Science, Part A: Polymer Chemistry   Check publisher's open access policy
ISSN 0887-624X
1099-0518
Publication date 1997-04-01
Sub-type Article (original research)
DOI 10.1002/(SICI)1099-0518(19970415)35:5<859::AID-POLA2>3.0.CO;2-G
Volume 35
Issue 5
Start page 859
End page 878
Total pages 20
Place of publication Hoboken, NJ, United States
Publisher John Wiley & Sons
Language eng
Abstract The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data.
Keyword Free-radical polymerization
Kinetics
Monomer
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ
Additional Notes Article first published online: 21 January 2000.

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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Created: Tue, 08 Mar 2011, 01:48:52 EST