Thin cyclomatrix polyphosphazene films: Interfacial polymerization of hexachlorocyclotriphosphazene with aromatic biphenols

Evelien Maaskant, Hubert Gojzewski, Mark A. Hempenius, G. Julius Vancso, Nieck E. Benes* (Corresponding Author)

*Corresponding author for this work

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Abstract

A series of thin cyclomatrix polyphosphazene films has been prepared by interfacial polymerization of hexachlorocyclotriphosphazene (HCCP) with an aromatic biphenol. The pKa values of the biphenol used strongly influence the properties of the hyper-cross-linked films formed. 4,4′-Dihydroxybiphenyl (BPH) and 4,4′-dihydroxydiphenyl ether (DHPE) possess pKa values in the range of 9.4-9.6 & 10.0-10.3 for the mono- and di-ionized forms, respectively, and produce films with a lower cross-link density, whereas 4,4′-dihydroxybenzophenone (DHBP) and 4,4′-sulfonyldiphenol (BPS) feature lower pKa values (7.4-7.6 & 8.0-8.2), resulting in films with a higher cross-link density. The difference in cross-link density is reflected in, e.g., the surface morphology and mechanical properties of the films. Mechanical stiffness has been quantitatively assessed by PeakForce QNM AFM. Lower cross-link densities result in Young's moduli with average values of 44-69 MPa, with a sharp distribution, while higher cross-link densities yield broadly distributed Young's moduli with average values of 255-306 MPa, depending on the choice of the biphenol. The surface chemistry of the films was successfully altered by post-functionalization.

Original languageEnglish
Pages (from-to)3169-3180
Number of pages12
JournalPolymer chemistry
Volume9
Issue number22
DOIs
Publication statusPublished - 14 Jun 2018

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Elastic Modulus
Polymerization
Ether
Elastic moduli
Surface chemistry
Surface morphology
poly(phosphazene)
hexachlorocyclotriphosphazene
Ethers
Stiffness
Mechanical properties

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title = "Thin cyclomatrix polyphosphazene films: Interfacial polymerization of hexachlorocyclotriphosphazene with aromatic biphenols",
abstract = "A series of thin cyclomatrix polyphosphazene films has been prepared by interfacial polymerization of hexachlorocyclotriphosphazene (HCCP) with an aromatic biphenol. The pKa values of the biphenol used strongly influence the properties of the hyper-cross-linked films formed. 4,4′-Dihydroxybiphenyl (BPH) and 4,4′-dihydroxydiphenyl ether (DHPE) possess pKa values in the range of 9.4-9.6 & 10.0-10.3 for the mono- and di-ionized forms, respectively, and produce films with a lower cross-link density, whereas 4,4′-dihydroxybenzophenone (DHBP) and 4,4′-sulfonyldiphenol (BPS) feature lower pKa values (7.4-7.6 & 8.0-8.2), resulting in films with a higher cross-link density. The difference in cross-link density is reflected in, e.g., the surface morphology and mechanical properties of the films. Mechanical stiffness has been quantitatively assessed by PeakForce QNM AFM. Lower cross-link densities result in Young's moduli with average values of 44-69 MPa, with a sharp distribution, while higher cross-link densities yield broadly distributed Young's moduli with average values of 255-306 MPa, depending on the choice of the biphenol. The surface chemistry of the films was successfully altered by post-functionalization.",
author = "Evelien Maaskant and Hubert Gojzewski and Hempenius, {Mark A.} and Vancso, {G. Julius} and Benes, {Nieck E.}",
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T1 - Thin cyclomatrix polyphosphazene films

T2 - Interfacial polymerization of hexachlorocyclotriphosphazene with aromatic biphenols

AU - Maaskant, Evelien

AU - Gojzewski, Hubert

AU - Hempenius, Mark A.

AU - Vancso, G. Julius

AU - Benes, Nieck E.

PY - 2018/6/14

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N2 - A series of thin cyclomatrix polyphosphazene films has been prepared by interfacial polymerization of hexachlorocyclotriphosphazene (HCCP) with an aromatic biphenol. The pKa values of the biphenol used strongly influence the properties of the hyper-cross-linked films formed. 4,4′-Dihydroxybiphenyl (BPH) and 4,4′-dihydroxydiphenyl ether (DHPE) possess pKa values in the range of 9.4-9.6 & 10.0-10.3 for the mono- and di-ionized forms, respectively, and produce films with a lower cross-link density, whereas 4,4′-dihydroxybenzophenone (DHBP) and 4,4′-sulfonyldiphenol (BPS) feature lower pKa values (7.4-7.6 & 8.0-8.2), resulting in films with a higher cross-link density. The difference in cross-link density is reflected in, e.g., the surface morphology and mechanical properties of the films. Mechanical stiffness has been quantitatively assessed by PeakForce QNM AFM. Lower cross-link densities result in Young's moduli with average values of 44-69 MPa, with a sharp distribution, while higher cross-link densities yield broadly distributed Young's moduli with average values of 255-306 MPa, depending on the choice of the biphenol. The surface chemistry of the films was successfully altered by post-functionalization.

AB - A series of thin cyclomatrix polyphosphazene films has been prepared by interfacial polymerization of hexachlorocyclotriphosphazene (HCCP) with an aromatic biphenol. The pKa values of the biphenol used strongly influence the properties of the hyper-cross-linked films formed. 4,4′-Dihydroxybiphenyl (BPH) and 4,4′-dihydroxydiphenyl ether (DHPE) possess pKa values in the range of 9.4-9.6 & 10.0-10.3 for the mono- and di-ionized forms, respectively, and produce films with a lower cross-link density, whereas 4,4′-dihydroxybenzophenone (DHBP) and 4,4′-sulfonyldiphenol (BPS) feature lower pKa values (7.4-7.6 & 8.0-8.2), resulting in films with a higher cross-link density. The difference in cross-link density is reflected in, e.g., the surface morphology and mechanical properties of the films. Mechanical stiffness has been quantitatively assessed by PeakForce QNM AFM. Lower cross-link densities result in Young's moduli with average values of 44-69 MPa, with a sharp distribution, while higher cross-link densities yield broadly distributed Young's moduli with average values of 255-306 MPa, depending on the choice of the biphenol. The surface chemistry of the films was successfully altered by post-functionalization.

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