Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone

Three tin(II) butoxides, namely: tin(II) n-butoxide, Sn(n-OBu)2; tin(II) i-butoxide, Sn(i-OBu)2; and tin(II) t-butoxide, Sn(t-OBu)2 were synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerisation of e-caprolactone (CL) at 120 °C. Two different methods of synthes...

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Main Authors: Manita Dumklang, Nilobon Pattawong, Winita Punyodom, Puttinan Meepowpan, Robert Molloy, Mark Hoffman
Format: Journal
Published: 2018
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http://cmuir.cmu.ac.th/jspui/handle/6653943832/48880
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spelling th-cmuir.6653943832-488802018-08-16T02:18:18Z Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone Manita Dumklang Nilobon Pattawong Winita Punyodom Puttinan Meepowpan Robert Molloy Mark Hoffman Biochemistry, Genetics and Molecular Biology Chemistry Materials Science Mathematics Physics and Astronomy Three tin(II) butoxides, namely: tin(II) n-butoxide, Sn(n-OBu)2; tin(II) i-butoxide, Sn(i-OBu)2; and tin(II) t-butoxide, Sn(t-OBu)2 were synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerisation of e-caprolactone (CL) at 120 °C. Two different methods of synthesis were compared: an old well-established method which gave solid products and a new modified method which, in the case of Sn(n-OBu)2, gave a novel liquid product. The liquid Sn(n-OBu)2 had the advantage for initiation purposes of being much more soluble than the solid Sn(n-OBu)2 due to its lower degree of molecular aggregation, a common characteristic of tin(II) alkoxides which limits their usefulness. Kinetic studies of CL polymerisation by dilatometry showed that the liquid Sn(n-OBu)2 initiator gave a much faster reaction with a higher first-order rate constant (kp = 8.25 l mol-1 min-1) than the solid Sn(n-OBu)2 initiator (kp = 2.96 l mol-1 min-1). The molecular weight of the polymer formed was also hi her. Increasing the bulkiness of the OBu group resulted in solid products with decreased solubility and initiating efficiency (for Sn(i-OBu)2, kp = 2.20 l mol-1 min-1; for Sn(t-OBu)2, kp = 0.69 l mol-1 min-1). It is concluded that the new modified method of initiator synthesis is capable of producing soluble tin(II) alkoxides which have the potential to offer improved kinetic and molecular weight control in the ring-opening polymerisation of cyclic esters. 2018-08-16T02:06:12Z 2018-08-16T02:06:12Z 2009-05-01 Journal 01252526 2-s2.0-67650666146 https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=67650666146&origin=inward http://cmuir.cmu.ac.th/jspui/handle/6653943832/48880
institution Chiang Mai University
building Chiang Mai University Library
country Thailand
collection CMU Intellectual Repository
topic Biochemistry, Genetics and Molecular Biology
Chemistry
Materials Science
Mathematics
Physics and Astronomy
spellingShingle Biochemistry, Genetics and Molecular Biology
Chemistry
Materials Science
Mathematics
Physics and Astronomy
Manita Dumklang
Nilobon Pattawong
Winita Punyodom
Puttinan Meepowpan
Robert Molloy
Mark Hoffman
Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
description Three tin(II) butoxides, namely: tin(II) n-butoxide, Sn(n-OBu)2; tin(II) i-butoxide, Sn(i-OBu)2; and tin(II) t-butoxide, Sn(t-OBu)2 were synthesized for use as coordination-insertion initiators in the bulk ring-opening polymerisation of e-caprolactone (CL) at 120 °C. Two different methods of synthesis were compared: an old well-established method which gave solid products and a new modified method which, in the case of Sn(n-OBu)2, gave a novel liquid product. The liquid Sn(n-OBu)2 had the advantage for initiation purposes of being much more soluble than the solid Sn(n-OBu)2 due to its lower degree of molecular aggregation, a common characteristic of tin(II) alkoxides which limits their usefulness. Kinetic studies of CL polymerisation by dilatometry showed that the liquid Sn(n-OBu)2 initiator gave a much faster reaction with a higher first-order rate constant (kp = 8.25 l mol-1 min-1) than the solid Sn(n-OBu)2 initiator (kp = 2.96 l mol-1 min-1). The molecular weight of the polymer formed was also hi her. Increasing the bulkiness of the OBu group resulted in solid products with decreased solubility and initiating efficiency (for Sn(i-OBu)2, kp = 2.20 l mol-1 min-1; for Sn(t-OBu)2, kp = 0.69 l mol-1 min-1). It is concluded that the new modified method of initiator synthesis is capable of producing soluble tin(II) alkoxides which have the potential to offer improved kinetic and molecular weight control in the ring-opening polymerisation of cyclic esters.
format Journal
author Manita Dumklang
Nilobon Pattawong
Winita Punyodom
Puttinan Meepowpan
Robert Molloy
Mark Hoffman
author_facet Manita Dumklang
Nilobon Pattawong
Winita Punyodom
Puttinan Meepowpan
Robert Molloy
Mark Hoffman
author_sort Manita Dumklang
title Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
title_short Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
title_full Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
title_fullStr Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
title_full_unstemmed Novel tin(II) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
title_sort novel tin(ii) butoxides for use as initiators in the ring-opening polymerisation of e-caprolactone
publishDate 2018
url https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=67650666146&origin=inward
http://cmuir.cmu.ac.th/jspui/handle/6653943832/48880
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