Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene
Abstract Bisphenol A was polycondensed with diphosgene in a dichloromethane/aqueous NaOH system. Temperature, time, and molar ratios of the reactants were optimized according to a previously elaborated optimization of the hydrolytic polycondensation of bisphenol A bischloroformate. Five of the follo...
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crwiley:10.1002/pola.10507 2024-06-02T08:05:12+00:00 Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene Kricheldorf, Hans R. Schwarz, Gert Böhme, Sigrid Schultz, Claus‐Ludolf 2003 http://dx.doi.org/10.1002/pola.10507 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpola.10507 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.10507 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Journal of Polymer Science Part A: Polymer Chemistry volume 41, issue 7, page 890-904 ISSN 0887-624X 1099-0518 journal-article 2003 crwiley https://doi.org/10.1002/pola.10507 2024-05-03T12:02:59Z Abstract Bisphenol A was polycondensed with diphosgene in a dichloromethane/aqueous NaOH system. Temperature, time, and molar ratios of the reactants were optimized according to a previously elaborated optimization of the hydrolytic polycondensation of bisphenol A bischloroformate. Five of the following catalysts were examined: triethylamine, 4‐( N , N ‐dimethylamino)pyridine (DMAP), ethyldiisopropylamine (EDPA), tetrabutylammonium hydrogen sulfate, and triethylbenzylammonium chloride (TEBA‐Cl). Triethylamine and DMAP accelerated the hydrolysis of diphosgene by formation of a hydrophilic acylammonium salt. Therefore, the molecular weights decreased with higher concentration of these tert ‐amines. However, the molecular weights increased (weight‐average molecular weight up to 10 6 ) with higher concentrations of tetraalkylammonium salts because these catalysts favor chain growth in the organic phase via “naked” phenoxide ions without catalyzing the hydrolysis of diphosgene. EDPA gave poor results under all circumstances. Cyclic polycarbonates were discovered in all samples. Their fraction increased with the average molecular weight of the samples. When samples prepared with triethylamine or TEBA‐Cl were fractionated, cycles having molar masses up to 15,000 Da were detected by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 890–904, 2003 Article in Journal/Newspaper Carbonic acid Wiley Online Library Journal of Polymer Science Part A: Polymer Chemistry 41 7 890 904 |
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Abstract Bisphenol A was polycondensed with diphosgene in a dichloromethane/aqueous NaOH system. Temperature, time, and molar ratios of the reactants were optimized according to a previously elaborated optimization of the hydrolytic polycondensation of bisphenol A bischloroformate. Five of the following catalysts were examined: triethylamine, 4‐( N , N ‐dimethylamino)pyridine (DMAP), ethyldiisopropylamine (EDPA), tetrabutylammonium hydrogen sulfate, and triethylbenzylammonium chloride (TEBA‐Cl). Triethylamine and DMAP accelerated the hydrolysis of diphosgene by formation of a hydrophilic acylammonium salt. Therefore, the molecular weights decreased with higher concentration of these tert ‐amines. However, the molecular weights increased (weight‐average molecular weight up to 10 6 ) with higher concentrations of tetraalkylammonium salts because these catalysts favor chain growth in the organic phase via “naked” phenoxide ions without catalyzing the hydrolysis of diphosgene. EDPA gave poor results under all circumstances. Cyclic polycarbonates were discovered in all samples. Their fraction increased with the average molecular weight of the samples. When samples prepared with triethylamine or TEBA‐Cl were fractionated, cycles having molar masses up to 15,000 Da were detected by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 890–904, 2003 |
format |
Article in Journal/Newspaper |
author |
Kricheldorf, Hans R. Schwarz, Gert Böhme, Sigrid Schultz, Claus‐Ludolf |
spellingShingle |
Kricheldorf, Hans R. Schwarz, Gert Böhme, Sigrid Schultz, Claus‐Ludolf Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
author_facet |
Kricheldorf, Hans R. Schwarz, Gert Böhme, Sigrid Schultz, Claus‐Ludolf |
author_sort |
Kricheldorf, Hans R. |
title |
Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
title_short |
Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
title_full |
Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
title_fullStr |
Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
title_full_unstemmed |
Polymers of carbonic acid 32: Influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol A with diphosgene |
title_sort |
polymers of carbonic acid 32: influence of catalysts on propagation and cyclization in the interfacial polycondensation of bisphenol a with diphosgene |
publisher |
Wiley |
publishDate |
2003 |
url |
http://dx.doi.org/10.1002/pola.10507 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fpola.10507 https://onlinelibrary.wiley.com/doi/pdf/10.1002/pola.10507 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Journal of Polymer Science Part A: Polymer Chemistry volume 41, issue 7, page 890-904 ISSN 0887-624X 1099-0518 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/pola.10507 |
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Journal of Polymer Science Part A: Polymer Chemistry |
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41 |
container_issue |
7 |
container_start_page |
890 |
op_container_end_page |
904 |
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1800749993699573760 |