The kinetics of crystallization of poly(ε-caprolactone) measured by FTIR spectroscopy

Phillipson, Kate; Jenkins, Michael J.; Hay, J. N.

doi:10.1007/s10973-015-5047-5

Cited by 14 publications

(14 citation statements)

References 23 publications

(27 reference statements)

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“…The isothermal crystallization kinetics of poly(ethylene terephthalate)-PET, poly(caprolactone)-PCL, and a stereo-copolymer of poly(Llactic acid)-scPLA, with 4% D-isomer have been studied by FTIR Experimental procedures and polymer characteristics are described [10][11][12][13] elsewhere in detail.…”

Section: Methodsmentioning

confidence: 99%

“…Local segments are not constrained by the tube or entanglements and the mean square displacement is proportional to square root of time. The development of secondary crystallization followed a square root dependence on the lapsed time and as a result local diffusion of the chain segments play a part in the nucleation of the secondary growth nuclei.…”

Section: Introductionmentioning

confidence: 99%

“…PET. The dependence of the average stem length on the square root of the lapsed time X t v t data using Equation13 and the degree of fit to the experimental data of X t against time was determined from a comparison with the calculated values from Equation13. The fit was within the error in measuring the X t , as can be seen inFigure 5.…”

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confidence: 96%

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Secondary crystallization kinetics

Hay

2018

Polymer Crystallization

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The overlap between primary and secondary crystallization is the cause of the repeated observations of fractional constant n values, of no theoretical significance, in the analysis of polymer crystallization by the Avrami equation. The time dependence of the growth nuclei in primary and secondary crystallization are explained in terms of reptation and nucleation theory. A composite equation involving both primary and secondary crystallization has been derived to account for the development of the total fractional crystallinity, Xt, with time, Xt = Xp,∞ (1–exp (–Zptn).(1 + ks t1/2) and procedures derived for determining the rate constants, Zp and ks, and the limiting fractional crystallinity of the primary process, Xp,∞, such that they are not treated as adjustable parameters. The fit of the equation to experimental crystallinity/time data was within experimental error. This interpretation accounted for n values in excess of those expected for the crystallization mechanisms adopted in deriving the Avrami equation but values >3.5 and <4.0 are attributed to the presence of induction times due to homogeneous primary nucleation of the lamellae. Evidence is presented for the presence of two simultaneous processes, primary and secondary, in the crystallization of polymers, which occur with different mechanisms and are readily distinguished by their dependence on time: an exponential increase and an increase with the square root of time. Differences arise from the critical growth nuclei, whose growth is limited by chain entanglements in the case of primary and local reptation in the case of secondary.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Secondary crystallization kinetics

Hay

2018

Polymer Crystallization

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“…Constant values in excess of those expected for the crystallization mechanisms are due to the additional crystallinity developed by the secondary process. In order to consider the generality of this phenomenon recent evaluation of the kinetics of crystallization of poly (є-caprolactone), which placed emphasis on measuring the secondary crystallization separately and in detail [2,3] have been reconsidered in the light of these observations.…”

Section: Introductionmentioning

confidence: 99%

The effect of a secondary process on crystallization kinetics – Poly (є-caprolactone) revisited

Phillipson

Jenkins

Hay

2016

European Polymer Journal

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Where a licence is displayed above, please note the terms and conditions of the licence govern your use of this document. When citing, please reference the published version. Take down policy While the University of Birmingham exercises care and attention in making items available there are rare occasions when an item has been uploaded in error or has been deemed to be commercially or otherwise sensitive.

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“…The decomposition temperatures are above 250 °C for every PCL obtained. FT‐IR and 1 H NMR spectrum of the PCL products (Figures S27‐S28) exhibit absorption bands and typical signals for linear PCL with a hydroxymethylene as terminal group ,…”

Section: Resultsmentioning

confidence: 99%

Copper(II) Complexes with Tridentate Bis(pyrazolylmethyl)pyridine Ligands: Synthesis, X‐ray Crystal Structures and ϵ‐Caprolactone Polymerization

et al. 2017

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Reactions of Cu(ClO4)2⋅6H2O with 2,6‐bis(3,5‐dimethylpirazol‐1‐ylmethyl)pyridine (dmpz‐py) (1), 2,6‐bis(4‐iodo‐3,5‐dimethylpirazol‐1‐ylmethyl)pyridine (I‐dmpz‐py) (2) and 2,6‐bis(4‐nitro‐3,5‐dimethylpirazol‐1‐ylmethyl)pyridine (NO2‐dmpz‐py) (3) yield the corresponding metal complexes: [Cu(dmpz‐py)(H2O)(ClO4)]ClO4 (4), [Cu(I‐dmpz‐py)(H2O)](ClO4)2 (5) and [Cu(NO2‐dmpz‐py)(H2O)(ClO4)2] (6). The complexes were isolated in high yields as stable solids at room temperature and characterized by melting point, electrical conductivity, and infrared and ultraviolet/visible spectroscopy. In addition, the crystal structures of the new complexes were determined by single‐crystal X‐ray diffraction and showed square‐base pyramidal (4), distorted square‐planar (5) and octahedral (6) geometries. All three complexes were active in the ring opening polymerization of ϵ‐caprolactone under solvent‐free conditions, producing polycaprolactones of narrow polydispersity and high crystallinity. The results obtained show an important increase in polymerization speed compared with analogous azole‐derived copper (II) complexes.

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The kinetics of crystallization of poly(ε-caprolactone) measured by FTIR spectroscopy

Cited by 14 publications

References 23 publications

Secondary crystallization kinetics

Secondary crystallization kinetics

The effect of a secondary process on crystallization kinetics – Poly (є-caprolactone) revisited

Copper(II) Complexes with Tridentate Bis(pyrazolylmethyl)pyridine Ligands: Synthesis, X‐ray Crystal Structures and ϵ‐Caprolactone Polymerization

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