Non-Isothermal Crystallization of Hyperbranched Poly(ε-caprolactone)s and Their Linear Counterpart

Three hyperbranched poly(ε‐caprolactone)s were prepared with the architectural variation in the length of linear backbone segments consisting of 5, 10, and 20 ε‐caprolactone units (accordingly given the names HPCL–5, –10, and –20, respectively) and in the number of branching points as characterized...

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Published in:Macromolecular chemistry and physics 2006-07, Vol.207 (13), p.1166-1173
Main Authors: Choi, Jeongsoo, Chun, Sang-Wook, Kwak, Seung-Yeop
Format: Article
Language:English
Subjects:
Applied sciences
Crystallization
Exact sciences and technology
hyperbranched
Organic polymers
Physicochemistry of polymers
poly(ε-caprolactone)
Properties and characterization
structure-property relations
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container_title Macromolecular chemistry and physics
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creator Choi, Jeongsoo
Chun, Sang-Wook
Kwak, Seung-Yeop
description Three hyperbranched poly(ε‐caprolactone)s were prepared with the architectural variation in the length of linear backbone segments consisting of 5, 10, and 20 ε‐caprolactone units (accordingly given the names HPCL–5, –10, and –20, respectively) and in the number of branching points as characterized by 1H NMR end group analyses. The non‐isothermal crystallizations of HPCLs and LPCL were performed using DSC at various cooling rates and the kinetic study was further performed by using both Ozawa and Kissinger methods. All the kinetic parameters such as the cooling functions and the apparent activation energy of crystallization indicated that HPCLs with longer linear segments and fewer number of branching points showed faster crystallization rates, whereas LPCL exhibited an intermediate rate between HPCL–10 and HPCL–20, i.e., HPCL–5 
doi_str_mv 10.1002/macp.200600129
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The non‐isothermal crystallizations of HPCLs and LPCL were performed using DSC at various cooling rates and the kinetic study was further performed by using both Ozawa and Kissinger methods. All the kinetic parameters such as the cooling functions and the apparent activation energy of crystallization indicated that HPCLs with longer linear segments and fewer number of branching points showed faster crystallization rates, whereas LPCL exhibited an intermediate rate between HPCL–10 and HPCL–20, i.e., HPCL–5 &lt; HPCL–10 &lt; LPCL &lt; HPCL–20. The decrease in the crystallization rate is attributed to the presence of heterogeneous branching points in HPCLs with shorter segments, which hinders the regular chain packing to crystallize. In addition, the faster crystallization of HPCL–20 compared to LPCL was associated with the higher cooperative chain mobility in the melt. Schematic illustrations for HPCL and LPCL.</description><identifier>ISSN: 1022-1352</identifier><identifier>EISSN: 1521-3935</identifier><identifier>DOI: 10.1002/macp.200600129</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>Applied sciences ; Crystallization ; Exact sciences and technology ; hyperbranched ; Organic polymers ; Physicochemistry of polymers ; poly(ε-caprolactone) ; Properties and characterization ; structure-property relations</subject><ispartof>Macromolecular chemistry and physics, 2006-07, Vol.207 (13), p.1166-1173</ispartof><rights>Copyright © 2006 WILEY‐VCH Verlag GmbH &amp; Co. 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Chem. Phys</addtitle><date>2006-07-05</date><risdate>2006</risdate><volume>207</volume><issue>13</issue><spage>1166</spage><epage>1173</epage><pages>1166-1173</pages><issn>1022-1352</issn><eissn>1521-3935</eissn><abstract>Three hyperbranched poly(ε‐caprolactone)s were prepared with the architectural variation in the length of linear backbone segments consisting of 5, 10, and 20 ε‐caprolactone units (accordingly given the names HPCL–5, –10, and –20, respectively) and in the number of branching points as characterized by 1H NMR end group analyses. The non‐isothermal crystallizations of HPCLs and LPCL were performed using DSC at various cooling rates and the kinetic study was further performed by using both Ozawa and Kissinger methods. All the kinetic parameters such as the cooling functions and the apparent activation energy of crystallization indicated that HPCLs with longer linear segments and fewer number of branching points showed faster crystallization rates, whereas LPCL exhibited an intermediate rate between HPCL–10 and HPCL–20, i.e., HPCL–5 &lt; HPCL–10 &lt; LPCL &lt; HPCL–20. The decrease in the crystallization rate is attributed to the presence of heterogeneous branching points in HPCLs with shorter segments, which hinders the regular chain packing to crystallize. In addition, the faster crystallization of HPCL–20 compared to LPCL was associated with the higher cooperative chain mobility in the melt. Schematic illustrations for HPCL and LPCL.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><doi>10.1002/macp.200600129</doi><tpages>8</tpages></addata></record>
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subjects Applied sciences
Crystallization
Exact sciences and technology
hyperbranched
Organic polymers
Physicochemistry of polymers
poly(ε-caprolactone)
Properties and characterization
structure-property relations
title Non-Isothermal Crystallization of Hyperbranched Poly(ε-caprolactone)s and Their Linear Counterpart
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