Kinetic study of the initiation reaction by a dilithium initiator used for the preparation of ABA triblock copolymers in non-polar medium
The kinetics of the reaction of the bifunctional lithium initiator, Li-DIB-Li, with DPE was studied. It was shown that the kinetic order of this reaction with respect to the reactive ends of the dilithium initiator is close to zero, indicating a rather high degree of aggregation of the dilithium ini...
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Veröffentlicht in: | Polymer (Guilford) 2009-11, Vol.50 (23), p.5368-5373 |
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creator | Janssens, Kristof Loozen, Els Yakimansky, Alexander Van Beylen, Marcel |
description | The kinetics of the reaction of the bifunctional lithium initiator, Li-DIB-Li, with DPE was studied. It was shown that the kinetic order of this reaction with respect to the reactive ends of the dilithium initiator is close to zero, indicating a rather high degree of aggregation of the dilithium initiator. Possible structures of these highly aggregated species are illustrated by DFT quantum-chemical calculations and their relative stabilities are analyzed. It is concluded that the solubilization through breaking up of long intermolecular aggregates of dilithium initiator chains into small soluble ones by complexation with durene is certainly as important or more than the dissociation of the active centers of the dilithium initiator, as originally thought.
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doi_str_mv | 10.1016/j.polymer.2009.09.045 |
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[Display omitted]</description><subject>Anionic polymerization</subject><subject>Bifunctional Li-initiators</subject><subject>Triblock copolymers</subject><issn>0032-3861</issn><issn>1873-2291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNqFkMtqHDEQRUWIIRMnnxDQJt71RK9-rcLE-BFiyMZeC3WpGmvS3WpLasN8gv_a6szE20CBSnDurapLyBfOtpzx6tt-O_vhMGLYCsba7VqqfEc2vKllIUTL35MNY1IUsqn4B_Ixxj1jTJRCbcjLLzdhckBjWuyB-p6mR6RucsmZ5PxEAxr423QHaqh1g0uPbhn_IT7QJaKlfW5W5RxwNuEozWa7HzuagusGD38o-NOeMavp5Kci_02gI9rs-Imc9WaI-Pn0npOH66v7y9vi7vfNz8vdXQGyZqmoDAJwa8qOqRqg7aoKgVdWqh4VQtewBljJG2Ur0UglUUhVC9u2zNSKWybPycXRdw7-acGY9Ogi4DCYCf0StVRty0UtM1geQQg-xoC9noMbTThozvQavN7r00F6DV6vpcqs-3oaYCKYoQ9mAhffxEJwplTDM_f9yGG-9tlllwgOJ8hpBISkrXf_mfQKJACe2w</recordid><startdate>20091103</startdate><enddate>20091103</enddate><creator>Janssens, Kristof</creator><creator>Loozen, Els</creator><creator>Yakimansky, Alexander</creator><creator>Van Beylen, Marcel</creator><general>Elsevier Ltd</general><general>Elsevier</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>F28</scope><scope>FR3</scope><scope>JG9</scope></search><sort><creationdate>20091103</creationdate><title>Kinetic study of the initiation reaction by a dilithium initiator used for the preparation of ABA triblock copolymers in non-polar medium</title><author>Janssens, Kristof ; Loozen, Els ; Yakimansky, Alexander ; Van Beylen, Marcel</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c370t-6aecc1da5b047cc9b66ec16d34fe4ecb808c05184d628343e23472d990a741d03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>Anionic polymerization</topic><topic>Bifunctional Li-initiators</topic><topic>Triblock copolymers</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Janssens, Kristof</creatorcontrib><creatorcontrib>Loozen, Els</creatorcontrib><creatorcontrib>Yakimansky, Alexander</creatorcontrib><creatorcontrib>Van Beylen, Marcel</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer (Guilford)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Janssens, Kristof</au><au>Loozen, Els</au><au>Yakimansky, Alexander</au><au>Van Beylen, Marcel</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetic study of the initiation reaction by a dilithium initiator used for the preparation of ABA triblock copolymers in non-polar medium</atitle><jtitle>Polymer (Guilford)</jtitle><date>2009-11-03</date><risdate>2009</risdate><volume>50</volume><issue>23</issue><spage>5368</spage><epage>5373</epage><pages>5368-5373</pages><issn>0032-3861</issn><eissn>1873-2291</eissn><coden>POLMAG</coden><abstract>The kinetics of the reaction of the bifunctional lithium initiator, Li-DIB-Li, with DPE was studied. It was shown that the kinetic order of this reaction with respect to the reactive ends of the dilithium initiator is close to zero, indicating a rather high degree of aggregation of the dilithium initiator. Possible structures of these highly aggregated species are illustrated by DFT quantum-chemical calculations and their relative stabilities are analyzed. It is concluded that the solubilization through breaking up of long intermolecular aggregates of dilithium initiator chains into small soluble ones by complexation with durene is certainly as important or more than the dissociation of the active centers of the dilithium initiator, as originally thought.
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subjects | Anionic polymerization Bifunctional Li-initiators Triblock copolymers |
title | Kinetic study of the initiation reaction by a dilithium initiator used for the preparation of ABA triblock copolymers in non-polar medium |
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