Effect of hydrogen substitution on the mass spectrometry and size-exclusion chromatography of perfluorinated polyether fluids as determined by time-of-flight secondary ion mass spectrometry

Hues, Steven M.; Wyatt, J. R.; Colton, Richard J.; Black, Bruce H.

doi:10.1021/ac00209a021

Cited by 8 publications

(8 citation statements)

References 22 publications

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“…Analysis of PFPEs present on solid surfaces as lubricants is a task of greater challenge. To this end, significant success in the understanding of surface-bound PFPEs has been obtained using static secondary ion mass spectrometry (SSIMS). − In particular, SSIMS has been used to quantify thin (<3 nm) PFPE layers 9,10 and to determine the average molecular weight ( M n ) from the relative intensities of peaks in the fragmentation patterns …”

Section: Introductionmentioning

confidence: 99%

Perfluoropolyethers: Analysis by TOF-SIMS

Spool¹,

Kasai

1996

Macromolecules

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TOF-SIMS spectra of the following perfluoropolyethers (PFPEs) were analyzed: Demnum-S, Krytox, Fomblin-Z, perfluoropoly(dioxolane), perfluoropoly(tetramethylene oxide), and perfluoropoly(ethylene oxide). In each case, the PFPE produced an intense negative ion spectrum with simple patterns persisting into the high-mass region surpassing the mean MW of the polymer. In contrast, the positive ion spectra are much more complex and compressed toward the low-mass end. Totally unrelated formation mechanisms for the positive and negative ions are thus indicated. It is proposed and substantiated that the negative ion spectra are dominated by anions resulting from one-step dissociative electron capture at ether oxygens, R−O−R‘ + e- → R−O- + •R‘. The Demnum molecule, having locally symmetric ether oxygens, produces two major peaks in each repetitive fragmentation packet, equal in intensity but displaced by the mass difference of the two end groups. PFPEs with asymmetric ether oxygens produce negative ion spectra resulting from asymmetric cleavage. The negative ion pattern of Fomblin-Z can be accurately modeled with the dissociative electron capture at ether oxygens linking randomly distributed methylene and ethylene units. Other less intense peaks in the negative ion spectra of PFPEs result from multiple electron capture events and from polymer chains with anomalous end groups or intrachain units.

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Section: Introductionmentioning

confidence: 99%

Perfluoropolyethers: Analysis by TOF-SIMS

Spool¹,

Kasai

1996

Macromolecules

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“…In that case, a popular fluorinated solvent is 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113). [8,9] In the extreme case of perfluoropolymers, the range of applicable solvents is significantly restricted. As an example, perfluoro(2-butyltetrafluorofuran) is used for poly[perfluoro(4-vinyloxyl-1-butene)].…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, it is suitable for separation of polymers having similar structures and is often combined SEC to characterize two-dimensional distribution of CCD and MWD. However, none of the above HPLC studies involved polyfluorinated polymers, except for several reports on SEC [6][7][8][9][10][11][12][13] and another one on HPLC. The latter used liquefied carbon dioxide (CO 2 ).…”

Section: Introductionmentioning

confidence: 99%

Determination of Chemical Composition Distribution and Molecular Weight Distribution of Poly(2-(perfluoroalkyl)ethyl acrylate-co-alkyl acrylate) by High Performance Liquid Chromatography and Size Exclusion Chromatography

Isemura

Sato

Kawahara

et al. 2008

International Journal of Polymer Analysis and Characterization

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The molecular weight distribution (MWD) of poly(2-(perfluoroalkyl) ethyl acrylate-co-alkyl acrylate) can be determined by size exclusion chromatography (SEC) using an appropriate mobile phase such as a mixture of HCFC225 and THF; however, the chemical composition distribution (CCD) of the copolymer has not been elucidated. We developed an HPLC method for determining the CCD by using a silica-based column modified by polyfluorinated groups, a devised mobile phase gradient system, and an evaporative light scattering detector. In this system, polymers having perfluoroalkyl units are retained on the column through interaction between fluorinated groups and elute at longer retention times. It has become apparent that the copolymer has a broad and characteristic CCD of three components, consisting of fluorinated and non-fluorinated forms and their copolymer. Two-dimensional development of MWD and CCD of the copolymer, called cross-fractionation, is also examined and discussed.

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“…Generally, several fluorine-containing solvents have been applied to SEC. Popular solvents for the polyfluorinated polymers are, for example, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) [1,2], whose production was halted due to its role in stratospheric ozone depletion, hexafluoroisopropanol (HFIP), perfluorocarbons, and fluorine containing ethers. However, no solvent completely satisfies the above requisites.…”

Section: Introductionmentioning

confidence: 99%

“…This polymer is water and oil repellent and is widely used as a homopolymer or copolymer with non-fluorinated acrylate or vinyl monomers. Meanwhile, perfluoropolyethers (PFPEs), having outstanding characteristics as lubricants of magnetic recording media and aerospace engines, are dissolved in a limited number of fluorinated solvents such as CFC113 [1,2], perfluorobutyl alkyl ether, HFIP, and HCFC225s. Besides, the number average molecular weight (Mn) of PFPEs was conventionally obtained by 19 F NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%