Pressure-induced polymorphism of caprolactam: a neutron diffraction study

Ian Hutchison, Craig L. Bull, William G. Marshall, Andrew J. Urquhart, Iain D.H. Oswald

Research output: Contribution to journalArticle

Abstract

Caprolactam, a precursor to nylon-6 has been investigated as part of our studies into the polymerization of materials at high pressure. Single-crystal X-ray and neutron powder diffraction data have been used to explore the high-pressure phase behavior of caprolactam and we have observed two new high pressure solid forms. The transition between each of the forms requires a substantial rearrangement of the molecules and we observe that the kinetic barrier to the conversion can aid retention of phases beyond their region of stability. Form II of caprolactam shows a small pressure region of stability between 0.5 and 0.9 GPa with Form III being stable from 0.9 GPa to 5.4 GPa. The two high-pressure forms have a catemeric hydrogen-bonding pattern compared with the dimer interaction observed in the ambient pressure Form I. The interaction between the chains has a marked effect on the directions of maximal compressibility in the structure. Neither of the high-pressure forms can be recovered to ambient pressure and there is no evidence of any polymerization occurring.
LanguageEnglish
Article number2174
Number of pages16
JournalMolecules
Volume24
Issue number11
DOIs
Publication statusPublished - 10 Jun 2019

Fingerprint

Caprolactam
Neutron Diffraction
polymorphism
Neutron diffraction
Polymorphism
neutron diffraction
Pressure
polymerization
Polymerization
Nylon (trademark)
compressibility
Powder Diffraction
Neutron powder diffraction
dimers
interactions
Hydrogen Bonding
Phase behavior
neutrons
Compressibility
Dimers

Keywords

  • high-pressure single-crystal X-ray diffraction
  • high-pressure neutron diffraction
  • phase transitions
  • intermolecular interactions
  • energy frameworks

Cite this

Hutchison, Ian ; Bull, Craig L. ; Marshall, William G. ; Urquhart, Andrew J. ; Oswald, Iain D.H. / Pressure-induced polymorphism of caprolactam : a neutron diffraction study. In: Molecules. 2019 ; Vol. 24, No. 11.
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Pressure-induced polymorphism of caprolactam : a neutron diffraction study. / Hutchison, Ian; Bull, Craig L.; Marshall, William G.; Urquhart, Andrew J.; Oswald, Iain D.H.

In: Molecules, Vol. 24, No. 11, 2174, 10.06.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Pressure-induced polymorphism of caprolactam

T2 - Molecules

AU - Hutchison, Ian

AU - Bull, Craig L.

AU - Marshall, William G.

AU - Urquhart, Andrew J.

AU - Oswald, Iain D.H.

PY - 2019/6/10

Y1 - 2019/6/10

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AB - Caprolactam, a precursor to nylon-6 has been investigated as part of our studies into the polymerization of materials at high pressure. Single-crystal X-ray and neutron powder diffraction data have been used to explore the high-pressure phase behavior of caprolactam and we have observed two new high pressure solid forms. The transition between each of the forms requires a substantial rearrangement of the molecules and we observe that the kinetic barrier to the conversion can aid retention of phases beyond their region of stability. Form II of caprolactam shows a small pressure region of stability between 0.5 and 0.9 GPa with Form III being stable from 0.9 GPa to 5.4 GPa. The two high-pressure forms have a catemeric hydrogen-bonding pattern compared with the dimer interaction observed in the ambient pressure Form I. The interaction between the chains has a marked effect on the directions of maximal compressibility in the structure. Neither of the high-pressure forms can be recovered to ambient pressure and there is no evidence of any polymerization occurring.

KW - high-pressure single-crystal X-ray diffraction

KW - high-pressure neutron diffraction

KW - phase transitions

KW - intermolecular interactions

KW - energy frameworks

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