Anionic Polymerization Mechanism of Acrylonitrile Trimer Anions : Key Branching Point between Cyclization and Chain Propagation
Journal of Physical Chemistry A Volume 116 Issue 30
Page 7937-7942
published_at 2012-08-02
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| File | |
| Title ( eng ) |
Anionic Polymerization Mechanism of Acrylonitrile Trimer Anions : Key Branching Point between Cyclization and Chain Propagation
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| Creator |
Ohshimo Keijiro
Ohno Koichi
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| Source Title |
Journal of Physical Chemistry A
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| Volume | 116 |
| Issue | 30 |
| Start Page | 7937 |
| End Page | 7942 |
| Abstract |
A cluster anion of vinyl compounds in the gaseous phase has served as one of the simplest microscopic models of the initial stages of anionic polymerization. Herein, we describe our investigations into the initial stage mechanisms of anionic polymerization of acrylonitrile (AN; CH2=CHCN) trimer anions. While the cyclic oligomer is found in mass and photoelectron spectroscopic studies of (AN)3-, only the chain oligomer is found in the infrared photodissociation (IRPD) spectrum of Ar-tagged (AN)3-. Based on the calculated polymerization pathway of (AN)3-, we consider that the chain oligomers are the reaction intermediates in the cyclization of (AN)3-. The rotational isomerization of the (AN)3- chain oligomer is found to be the bottleneck in the cyclization of (AN)3-. To form the (AN)4- chain oligomer by chain propagation, the addition of an AN molecule to (AN)3- should occur prior to the rotational isomerization. We conclude that the rotational isomerization in the (AN)3- chain oligomer is the key branching point between cyclization (termination) or chain propagation in the anionic polymerization.
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| Keywords |
Intracluster reaction
cluster anions
infrared spectroscopy
reaction pathway
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| Descriptions |
This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2012, available online: http://pubs.acs.org/doi/abs/10.1021/jp305291r.
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| NDC |
Chemistry [ 430 ]
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| Language |
eng
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| Resource Type | journal article |
| Publisher |
American Chemical Society
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| Date of Issued | 2012-08-02 |
| Rights |
Copyright (c) 2012 American Chemical Society
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| Publish Type | Author’s Original |
| Access Rights | open access |
| Source Identifier |
[ISSN] 1089-5639
[DOI] 10.1021/jp305291r
[DOI] http://dx.doi.org/10.1021/jp305291r
isVersionOf
[PMID] 22775348
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