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Crystallization of Long-Spaced Precision Polyacetals III : Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes

Crystallization of Long-Spaced Precision Polyacetals III : Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes

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MARXSEN, Stephanie F., Manuel HÄUSSLER, Stefan MECKING, Rufina G. ALAMO, 2021. Crystallization of Long-Spaced Precision Polyacetals III : Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes. In: Polymers. MDPI. 13(10), 1560. eISSN 2073-4360. Available under: doi: 10.3390/polym13101560

@article{Marxsen2021-05-13Cryst-53978, title={Crystallization of Long-Spaced Precision Polyacetals III : Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes}, year={2021}, doi={10.3390/polym13101560}, number={10}, volume={13}, journal={Polymers}, author={Marxsen, Stephanie F. and Häußler, Manuel and Mecking, Stefan and Alamo, Rufina G.}, note={Article Number: 1560} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/53978"> <dc:contributor>Mecking, Stefan</dc:contributor> <dc:creator>Häußler, Manuel</dc:creator> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/53978/1/Marxsen_2-1cnj3nt4owf2s3.pdf"/> <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/53978/1/Marxsen_2-1cnj3nt4owf2s3.pdf"/> <dc:language>eng</dc:language> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:creator>Marxsen, Stephanie F.</dc:creator> <dc:contributor>Alamo, Rufina G.</dc:contributor> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dcterms:title>Crystallization of Long-Spaced Precision Polyacetals III : Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes</dcterms:title> <dc:contributor>Häußler, Manuel</dc:contributor> <dc:creator>Alamo, Rufina G.</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-06-15T14:25:02Z</dcterms:available> <dcterms:issued>2021-05-13</dcterms:issued> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2021-06-15T14:25:02Z</dc:date> <dc:rights>Attribution 4.0 International</dc:rights> <dc:creator>Mecking, Stefan</dc:creator> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/53978"/> <dc:contributor>Marxsen, Stephanie F.</dc:contributor> <dcterms:abstract xml:lang="eng">In this paper we extend the study of polymorphism and crystallization kinetics of aliphatic polyacetals to include shorter (PA-6) and longer (PA-26) methylene lengths in a series of even long-spaced systems. On a deep quenching to 0 °C, the longest even polyacetals, PA-18 and PA-26, develop mesomorphic-like disordered structures which, on heating, transform progressively to hexagonal, Form I, and Form II crystallites. Shorter polyacetals, such as PA-6 and PA-12 cannot bypass the formation of Form I. In these systems a mixture of this form and disordered structures develops even under fast deep quenching. A prediction from melting points that Form II will not develop in polyacetals with eight or fewer methylene groups between consecutive acetals was further corroborated with data for PA-6. The temperature coefficient of the overall crystallization rate of the two highest temperature polymorphs, Form I and Form II, was analyzed from the differential scanning calorimetry (DSC) peak crystallization times. The crystallization rate of Form II shows a deep inversion at temperatures approaching the polymorphic transition region from above. The new data on PA-26 confirm that at the minimum rate the heat of fusion is so low that crystallization becomes basically extinguished. The rate inversion and dramatic drop in the heat of fusion irrespective of crystallization time are associated with a competition in nucleation between Forms I and II. The latter is due to large differences in nucleation barriers between these two phases. As PA-6 does not develop Form II, the rate data of this polyacetal display a continuous temperature gradient. The data of the extended polyacetal series demonstrate the important role of methylene sequence length on polymorphism and crystallization kinetics.</dcterms:abstract> <dcterms:rights rdf:resource="http://creativecommons.org/licenses/by/4.0/"/> </rdf:Description> </rdf:RDF>

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