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Kinetic and Mechanistic Studies of Bulk Copolymerization of L-lactide and Glycolide Initiated by Liquid Tin(II) n-Butoxide


Paper Type 
Contributed Paper
Title 
Kinetic and Mechanistic Studies of Bulk Copolymerization of L-lactide and Glycolide Initiated by Liquid Tin(II) n-Butoxide
Author 
Tawan Chaiwon, Montira Sriyai, Puttinan Meepowpan, Robert Molloy, Kanarat Nalampang, Narin Kaabbuathong and Winita Punyodom*
Email 
winitacmu@gmail.com
Abstract:

The main objective of this study was to investigate the effectiveness of liquid tin(II) n-butoxide

(Sn(On-Bu)2) as an initiator in the bulk ring-opening copolymerization (ROCP) of L-lactide (LL)
and glycolide (GL) in mol% ratio 80:20. The effects of initiator concentration and copolymerization
temperature on the kinetics of the reaction were studied by gravimetric analysis. The initiator concentrations
used were 0.010, 0.025, 0.050, 0.075 and 0.100 mol% while the copolymerizations were carried out
for 96 h at temperatures ranging from 120-150°C. Increasing the liquid Sn(On-Bu)2 initiator concentration
increased both the apparent first-order copolymerization rate constant (kapp) and the final %conversion.
The 0.075 mol% liquid Sn(On-Bu)2 concentration was chosen to study the effect of copolymerization
temperature. The results showed that kapp increased with increasing temperature as expected. A comparative
study between the liquid Sn(On-Bu)2 and the conventional initiating system of tin(II) 2-ethylhexanoate
(Sn(Oct)2) and n-butyl alcohol (n-BuOH) showed that the liquid Sn(On-Bu)2 gave a higher kapp under
the same conditions of copolymerization. Furthermore, copolymerization of LL and GL using
the liquid Sn(On-Bu)2 initiator resulted in a lower activation energy (Ea = 9.57 kJ mol-1) than that for
the Sn(Oct)2/n-BuOH system (Ea = 15.14 kJ mol-1). In terms of molecular weight, the liquid Sn(On-Bu)2
tended to yield poly(L-lactide-co-glycolide) (PLG) copolymers with higher molecular weights than
the Sn(Oct)2/n-BuOH system under the same conditions. These combined results showed that
the liquid Sn(On-Bu)2 was a highly effective initiator in the ROCP of LL and GL cyclic ester monomers
Start & End Page 
489 - 505
Received Date 
2020-09-12
Revised Date 
Accepted Date 
2020-12-02
Full Text 
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Keyword 
L-lactide, glycolide, ring-opening copolymerization, liquid tin(II) alkoxide, kinetics
Volume 
Vol.48 No.2 (March 2021)
DOI 
Citation 
Chaiwon T.,Sriyai M.,Meepowpan P.,Molloy R.,Nalampang K.,Kaabbuathong N., et al., Kinetic and Mechanistic Studies of Bulk Copolymerization of L-lactide and Glycolide Initiated by Liquid Tin(II) n-Butoxide, Chiang Mai Journal of Science, 2021; 48(2): 489-505.
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