Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators
Abstract Numerous BuSnCl , Bu 2 SnCl , and Bu 3 SnCl‐initiated polymerizations of cyclo(tri‐methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initia...
Published in: | Journal of Polymer Science Part A: Polymer Chemistry |
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crwiley:10.1002/pola.1995.080331313 2024-09-15T18:01:40+00:00 Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators Kricheldorf, Hans R. Weegen‐Schulz, Bettina 1995 http://dx.doi.org/10.1002/pola.1995.080331313 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpola.1995.080331313 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.1995.080331313 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Journal of Polymer Science Part A: Polymer Chemistry volume 33, issue 13, page 2193-2201 ISSN 0887-624X 1099-0518 journal-article 1995 crwiley https://doi.org/10.1002/pola.1995.080331313 2024-07-25T04:23:30Z Abstract Numerous BuSnCl , Bu 2 SnCl , and Bu 3 SnCl‐initiated polymerizations of cyclo(tri‐methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initiators, but their reactivities decrease in the order BuSnCl 3 > Bu 2 SnCl 2 > Bu 3 SnCl. The maximum molecular weights decrease in the same order. With BuSnCl 3 M w s up to 250,000 were obtained. These molecular weights were determined by GPC on the basis of the universal calibration method. In this connection Mark‐Houwink equations for two solvents, tetrahydrofuran (THF) and CH 2 Cl 2 were determined and compared with literature data. Furthermore, mechanistic aspects were studied. 1 H‐ and 13 C‐ NMR spectra revealed that BuSnCl 3 forms complexes with the CO‐group of TMC, whereas Bu 2 SnCl 3 do not cause NMR spectroscopic effects. Kinetic studies in chloroform and nitrobenzene and a comparison with Bu 3 SnOMe suggest that at least BuSnCl 3 initiates a cationic mechanism. However, in contrast to SnCl 4 (or SnBr 4 ), BuSnCl 3 does not cause decarboxylation. Regardless of the initiator 1 H‐NMR spectroscopy revealed CH 2 OH and CH 2 CI endgroups in all cases. © 1995 John Wiley & Sons, Inc. Article in Journal/Newspaper Carbonic acid Wiley Online Library Journal of Polymer Science Part A: Polymer Chemistry 33 13 2193 2201 |
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English |
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Abstract Numerous BuSnCl , Bu 2 SnCl , and Bu 3 SnCl‐initiated polymerizations of cyclo(tri‐methylene carbonate) (TMC) were conducted in bulk. In addition to the initiator, reaction time, temperature, and monomer/initiator (M/I) ratio were varied. Yields above 90% were obtained with all three initiators, but their reactivities decrease in the order BuSnCl 3 > Bu 2 SnCl 2 > Bu 3 SnCl. The maximum molecular weights decrease in the same order. With BuSnCl 3 M w s up to 250,000 were obtained. These molecular weights were determined by GPC on the basis of the universal calibration method. In this connection Mark‐Houwink equations for two solvents, tetrahydrofuran (THF) and CH 2 Cl 2 were determined and compared with literature data. Furthermore, mechanistic aspects were studied. 1 H‐ and 13 C‐ NMR spectra revealed that BuSnCl 3 forms complexes with the CO‐group of TMC, whereas Bu 2 SnCl 3 do not cause NMR spectroscopic effects. Kinetic studies in chloroform and nitrobenzene and a comparison with Bu 3 SnOMe suggest that at least BuSnCl 3 initiates a cationic mechanism. However, in contrast to SnCl 4 (or SnBr 4 ), BuSnCl 3 does not cause decarboxylation. Regardless of the initiator 1 H‐NMR spectroscopy revealed CH 2 OH and CH 2 CI endgroups in all cases. © 1995 John Wiley & Sons, Inc. |
format |
Article in Journal/Newspaper |
author |
Kricheldorf, Hans R. Weegen‐Schulz, Bettina |
spellingShingle |
Kricheldorf, Hans R. Weegen‐Schulz, Bettina Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
author_facet |
Kricheldorf, Hans R. Weegen‐Schulz, Bettina |
author_sort |
Kricheldorf, Hans R. |
title |
Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
title_short |
Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
title_full |
Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
title_fullStr |
Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
title_full_unstemmed |
Polymers of carbonic acid. XIV. High molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
title_sort |
polymers of carbonic acid. xiv. high molecular weight poly(trimethylene carbonate) by ring‐opening polymerization with butyltin chlorides as initiators |
publisher |
Wiley |
publishDate |
1995 |
url |
http://dx.doi.org/10.1002/pola.1995.080331313 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpola.1995.080331313 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.1995.080331313 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Journal of Polymer Science Part A: Polymer Chemistry volume 33, issue 13, page 2193-2201 ISSN 0887-624X 1099-0518 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/pola.1995.080331313 |
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Journal of Polymer Science Part A: Polymer Chemistry |
container_volume |
33 |
container_issue |
13 |
container_start_page |
2193 |
op_container_end_page |
2201 |
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1810438763083464704 |