Cleavage of Organosiloxanes with Dimethyl Carbonate : A Mild Approach To Graft-to-Surface Modification
In this work, we explore the depolymerization of poly(dimethylsiloxane) (PDMS-100) and poly(methylphenylsiloxane) (PMPS) using dimethyl carbonate (DMC) and develop a surface functionalization method by utilizing the DMC-imparted active methoxy end groups of the partially depolymerized polysiloxanes....
Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 34(2018), 33 vom: 21. Aug., Seite 9719-9730 |
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Weitere Verfasser: | , , , |
Format: | Online-Aufsatz |
Sprache: | English |
Veröffentlicht: |
2018
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Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
Schlagworte: | Journal Article Research Support, Non-U.S. Gov't |
Zusammenfassung: | In this work, we explore the depolymerization of poly(dimethylsiloxane) (PDMS-100) and poly(methylphenylsiloxane) (PMPS) using dimethyl carbonate (DMC) and develop a surface functionalization method by utilizing the DMC-imparted active methoxy end groups of the partially depolymerized polysiloxanes. The efficiency of dimethyl carbonate as a reagent for organosiloxane cleavage was confirmed by means of 1H NMR spectroscopy, size-exclusion chromatography, and viscosity measurements. The reaction of fumed silica with organosiloxanes (PMPS, PDMS-50) in the presence of DMC was investigated using the ζ-potential, 29Si and 13C solid-state NMR spectroscopy, IR spectroscopy, CHN analysis, contact angle goniometry, thermogravimetric analysis, scanning and transmission electron microscopy (TEM), and rheology. It was found that the interaction of PMPS/DMC with an SiO2 surface produced hydrophobic and thermally stable moieties (up to 550 °C) with a densely packed (average 2.2 groups/nm2) alkylsiloxane network for SiO2/PMPS + DMC in comparison with SiO2/PMPS (average 1.4 groups/nm2). Surface functionalization was successfully attained at a relatively moderate temperature of 200 °C. Scanning electron microscopy data show that the average size of aggregates of PMPS/DMC-modified silica nanoparticles is smaller than that of the initial silica and silica modified with neat PMPS. TEM images reveal uniform distribution of the PMPS/DMC mixture across the SiO2 surface. Rheology studies show thixotropic behavior in industrial oil (I-40A), a fully reversible nanostructure and shorter structure recovery time for fumed silica modified in the presence of DMC |
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Beschreibung: | Date Completed 17.10.2018 Date Revised 17.10.2018 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
ISSN: | 1520-5827 |
DOI: | 10.1021/acs.langmuir.8b01580 |