Insertion Polymerization of Divinyl Formal

Kurzanzeige
dc.contributor.authorJian, Zhongbao
dc.contributor.authorMecking, Stefan
dc.date.accessioned2016-07-13T08:38:30Z
dc.date.available2016-07-13T08:38:30Z
dc.date.issued2016-06-28eng
dc.description.abstractCopolymerization of ethylene and divinyl formal by [{κ2-P,O-(2-MeOC6H4)2PC6H4SO3}PdMe(dmso)] (1) by a coordination–insertion mechanism affords highly linear polyethylenes with a high (12.5 mol %) incorporation of divinyl formal. This significantly exceeds the thus far relatively low incorporation (6.9 mol %) and activity with vinyl ether monomer in insertion polymerization. The resulting ethylene–divinyl formal copolymers exclusively (>98%) contain five-membered (trans-1,3-dioxolane) and six-membered (cis-/trans-1,3-dioxane) cyclic acetal units in the main chain, and also in the initiating ends of this functionalized polyethylene. Comprehensive NMR analysis of the microstructure of these copolymers revealed that under pressure reactor conditions consecutive 2,1–1,2-insertion of divinyl formal into a Pd–H bond is preferred, but consecutive 1,2–1,2-insertion of divinyl formal into more bulky Pd–alkyls (growing polymer chain) is favored. Moreover, homopolymerization of divinyl formal yielded a non-cross-linking poly(divinyl formal) with degrees of polymerization of DPn ≈ 26.eng
dc.description.versionpublishedeng
dc.identifier.doi10.1021/acs.macromol.6b00983eng
dc.identifier.urihttps://kops.uni-konstanz.de/handle/123456789/34763
dc.language.isoengeng
dc.subject.ddc540eng
dc.titleInsertion Polymerization of Divinyl Formaleng
dc.typeJOURNAL_ARTICLEeng
dspace.entity.typePublication
kops.citation.bibtex
@article{Jian2016-06-28Inser-34763,
  year={2016},
  doi={10.1021/acs.macromol.6b00983},
  title={Insertion Polymerization of Divinyl Formal},
  number={12},
  volume={49},
  issn={0024-9297},
  journal={Macromolecules},
  pages={4395--4403},
  author={Jian, Zhongbao and Mecking, Stefan}
}
kops.citation.iso690JIAN, Zhongbao, Stefan MECKING, 2016. Insertion Polymerization of Divinyl Formal. In: Macromolecules. 2016, 49(12), pp. 4395-4403. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b00983deu
kops.citation.iso690JIAN, Zhongbao, Stefan MECKING, 2016. Insertion Polymerization of Divinyl Formal. In: Macromolecules. 2016, 49(12), pp. 4395-4403. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b00983eng
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    <dcterms:abstract xml:lang="eng">Copolymerization of ethylene and divinyl formal by [{κ&lt;sup&gt;2&lt;/sup&gt;-P,O-(2-MeOC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;PC&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;SO&lt;sub&gt;3&lt;/sub&gt;}PdMe(dmso)] (1) by a coordination–insertion mechanism affords highly linear polyethylenes with a high (12.5 mol %) incorporation of divinyl formal. This significantly exceeds the thus far relatively low incorporation (6.9 mol %) and activity with vinyl ether monomer in insertion polymerization. The resulting ethylene–divinyl formal copolymers exclusively (&gt;98%) contain five-membered (trans-1,3-dioxolane) and six-membered (cis-/trans-1,3-dioxane) cyclic acetal units in the main chain, and also in the initiating ends of this functionalized polyethylene. Comprehensive NMR analysis of the microstructure of these copolymers revealed that under pressure reactor conditions consecutive 2,1–1,2-insertion of divinyl formal into a Pd–H bond is preferred, but consecutive 1,2–1,2-insertion of divinyl formal into more bulky Pd–alkyls (growing polymer chain) is favored. Moreover, homopolymerization of divinyl formal yielded a non-cross-linking poly(divinyl formal) with degrees of polymerization of DP&lt;sub&gt;n&lt;/sub&gt; ≈ 26.</dcterms:abstract>
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kops.sourcefieldMacromolecules. 2016, <b>49</b>(12), pp. 4395-4403. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b00983deu
kops.sourcefield.plainMacromolecules. 2016, 49(12), pp. 4395-4403. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b00983deu
kops.sourcefield.plainMacromolecules. 2016, 49(12), pp. 4395-4403. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/acs.macromol.6b00983eng
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